Amine Tungstates and Lubricant Compositions

ABSTRACT

This invention relates to lubricating oil additives, and to lubricating oil compositions, their method of preparation, and use. More specifically, this invention relates to several novel lubricating oil additives and compositions which contain a tungsten compound and an antioxidant, namely aminic antioxidants such as a secondary diarylamine or an alkylated phenothiazine. The use of the tungsten compound with the secondary diarylamine and/or the alkylated phenothiazine provides improved oxidation and deposit control to lubricating oil compositions. The lubricating oil compositions of this invention are particularly useful as crankcase and transmission lubricants, gear oils and other high performance lubricant applications.

This application claims the benefit of priority to U.S. ProvisionalApplication 60/698,750, filed on Jul. 12, 2005. The contents of thisU.S. Provisional Application are hereby incorporated by reference in itsentirety.

FIELD OF THE INVENTION

This invention relates to lubricating oil additives, and to lubricatingoil compositions, their method of preparation, and use. Morespecifically, this invention relates to several novel lubricating oiladditives and compositions which contain a tungsten compound and anantioxidant, namely aminic antioxidants such as a secondary diarylamineor an alkylated phenothiazine. The use of the tungsten compound with thesecondary diarylamine and/or the alkylated phenothiazine providesimproved oxidation and deposit control to lubricating oil compositions.The lubricating oil compositions of this invention are particularlyuseful as crankcase and transmission lubricants, gear oils and otherhigh performance lubricant applications.

BACKGROUND OF THE INVENTION

Lubricating oils as used in, for example, the internal combustionengines of automobiles or trucks are subjected to a demandingenvironment during use. This environment results in the oxidation of theoil catalyzed by the presence of impurities in the oil, such as ironcompounds, and is also promoted by the elevated temperatures experiencedby the oil during use. This catalyzed oxidation of the oil not onlycontributes to the formation of corrosive oxidation products and sludgein the oil but can also cause the viscosity of the oil to increase oreven cause the oil to solidify. This oxidation of lubricating oilsduring use is usually controlled to some extent by the use ofantioxidant additives which may extend the useful life of the oil, forexample, by reducing or preventing unacceptable viscosity increases.

Aminic antioxidants are antioxidants that contain one or more nitrogenatoms, such as alkylated diphenyl amines and phenothiazines. Phenolicantioxidants contain one or more sterically hindered phenolfunctionalities, and can be either used alone or in synergisticcombinations with alkylated aminic antioxidants. The synthesis and usesof phenolic antioxidants, phenothiazines and aromatic amines have beenreported. Phenothiazine antioxidants have been used as a stand aloneadditive, chemically modified or grafted onto the backbone of polymers.

There is, however, a continuing need for new antioxidants andantioxidant systems which offer improved performance and which areeffective at low levels. There are a number of factors which havecontributed to this continuing need. One such factor is that in recentyears internal combustion engines are often operated at even highertemperatures, which tend to increase the rate of oxidation and shortenthe useful life of the oil. In addition, there is a strong desire to usecheaper base stocks for lubricating oil compositions which have inferiorresistance to oxidation and require more efficient and effectiveantioxidants. There is also a need for lubricating oils to have a longerin service life span to support the longer service intervals for motorvehicles. There is also a desire to find antioxidants and antioxidantsystems which meet the above requirements and at the same time are notdetrimental to other aspects of motor vehicle performance. In thisrespect there is a desire for antioxidants which do not contribute tothe phosphorus content of motor vehicle exhausts, as phosphorus isdetrimental to the performance of catalyst based exhaust purificationsystems. The trend to reduce phosphorus levels in the final formulationhas led to use of lower levels of zinc dialkyldithiophosphates, (ZDDP).This has led to an overall reduction in the levels of antioxidants usedin the final formulation because ZDDP also serves as an antioxidant, inaddition to an extreme-pressure/antiwear additive. The trend to reducethe total levels of sulfur in lubricants will also lead to lower uselevels of sulfur containing multifunctional antioxidant extreme-pressureadditives such as sulfurized olefins, and other sulfur containingdetergents. In addition some antioxidants, such as for examplediphenylamines, cannot be used at relatively high concentrations as thismay result in sedimentation or deposits in hot engine areas such as thediesel ring areas in diesel engines. The invention is concerned with theproblem of providing an improved antioxidant for use in lubricatingoils.

SUMMARY OF THE INVENTION

This invention relates to new tungsten containing lubricating oiladditives, compositions, their method of preparation, and use. Morespecifically, this invention relates to lubricating oil compositionswhich contain a tungsten compound and an aminic antioxidant such asalkylated diphenyl amines and/or alkylated phenothiazines. In additionthe composition may additionally include a sulfur-containing additivesuch as sulfurized olefins, sulfurized vegetable oils, sulfurized animalfats and oils, sulfurized fatty acids, sulfurized synthetic esters,sulfurized acrylates and sulfurized methacrylates, and sulfurizedsuccinic acid derivatives, thiadiazole, dithiocarbamate, dithiophosphateand mixtures thereof. The use of both the tungsten containing additiveand the alkylated secondary diarylamine, and alternatively further withphenothiazine, provides improved oxidation and deposit control tolubricating oil compositions. The lubricating oil compositions of thisinvention are particularly useful as crankcase and transmissionlubricants, gear oils and other high performance lubricant applications.

The antioxidant additive compositions of this invention result in lowlevels of deposits and display improved corrosion inhibition andfriction properties.

This invention provides compositions comprising certain tungstencontaining compounds and antioxidants, namely certain aromatic amines,either alone or in combination with phenolic antioxidants, that providea highly effective regenerative antioxidant system for use inlubricating oils, especially in lubricating oils for gasoline and dieselengines. Lubricating oils as used in the internal combustion engines andtransmissions of automobiles or trucks, gear oils and other hightemperature lubricant applications are subjected to a demandingenvironment during use. This environment results in the oxidation of oilwhich is catalyzed by the presence of impurities in the oil (such asiron compounds) and promoted by the elevated temperatures of the oilduring use.

DETAILED DESCRIPTION OF THE INVENTION

This invention provides compositions containing various amine tungstatecompounds and various amine additives which display synergisticallyenhanced friction reducing properties compared to previously reportedamine tungstate-based compositions that include sulfur or phosphoruscompounds and additional metallic additives.

It has been found that the combination of (1) an oil soluble ordispersible tungsten compound and (2) a secondary diarylamine, such asan alkylated diphenylamine, either alone or in combination with alsopreferably an alkylated, phenothiazine, is highly effective atcontrolling crankcase lubricant oxidation and deposit formation.Examples of the types of compounds that may be used in this inventionare described in the following. The tungsten compound may be usedbetween 20 and 4000 ppm, preferably between 20 to 1000 ppm, based on theamount of tungsten delivered to the finished lubricating oil. Alkylatedphenothiazines, secondary diarylamines, and other suitable aminicantioxidants may be used at concentrations ranging from 0.05 to 2.5 wt.% in the finished lubricant, preferably between 0.1 to 1.0 wt. %. Insome embodiments of the invention, an oil soluble or dispersiblemolybdenum compound may be substituted for the tungsten compound. Inaddition to the antioxidants of this invention, the lubricatingcomposition may also contain dispersants, detergents, anti-wearadditives including for example ZDDP, ashless dithiophosphates, ashlessphosphorothioates and thiophosphates, ashless dithiocarbamates,additional antioxidants if required, friction modifiers, corrosioninhibitors, anti-foaming additives, pour point depressants and viscosityindex improvers. The lubricant may be prepared from any paraffinic,naphthenic, aromatic, or synthetic base oil, or mixtures thereof. In anembodiment, the lubricant may contain between 250 and 1000 ppm ofphosphorus derived from ZDDP and between 500 and 3000 ppm of calciumfrom calcium containing sulfonate detergents or calcium containingphenate detergents. In this manner, both crankcase and automatictransmission fluid (ATF) lubricants, gear oils and other hightemperature lubricants are readily prepared.

Thus, one embodiment of the present invention provides crankcase andtransmission fluid lubricants, gear oils and other high temperatureindustrial lubricants and additive package concentrates, which containvery low levels of phosphorus. More preferred are lubricant compositionscontaining zero or essentially zero phosphorus. By “essentially zerophosphorus” herein is meant phosphorus levels of less than or equal toabout 100 ppm.

In another embodiment, the lubricant does not contain ZDDP, but maycontain other sources of phosphorus, including ashless dithiophosphates,

I. Tungsten Compounds of the Current Invention and their Preparation

1.0 Sulfur- and Phosphorus-Free Organotungsten Compounds

Sulfur- and phosphorus-free organotungsten compounds that are acomponent of the present invention may be prepared by reacting a sulfurand phosphorus-free tungsten source with an organic compound containingan amino group. Examples of sulfur- and phosphorus-free tungsten sourcesinclude tungstic acid, tungsten trioxide, ammonium ortho tungstate,ammonium para tungstate, ammonium meta tungstate, sodium tungstate andpotassium tungstate. The amino groups may be monoamines, diamines, orpolyamines, containing primary, secondary or tertiary aminefunctionalities. The primary amine structure may be

which R¹, R² and R³ are independently hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅alkyl interrupted by oxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkylwhich is unsubstituted or substituted by C₁-C₄ allyl and/or carboxyl;C₅-C₁₅ cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyland/or carboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl; —COR6, a5- or 6-membered heterocyclic ring which is unsubstituted or substitutedby C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; a 5- or 6-memberedheterocyclic ring which is benzo-fused and is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl.

For example, the secondary amine is of the following structure

wherein R⁴ and R⁵ are independently hydrogen, linear, branched,saturated or unsaturated alkyl of 1 to 40 carbon atoms, cycloalkyl of 5to 40 carbon atoms, aryl of 6 to 40 carbon atoms, aralkyl of 7 to 9carbon atoms, where the aralkyl may be substituted by alkyl of 1 to 36carbon atoms.

The tertiary amine is preferably represented by general formula

wherein R₁, R₂, and R₃ are independently each a C₁ to C₃₆ residue thatmay optionally contain at least one —O—, —S—, —SO—, —CO₂—, —CO—, or—CON— moiety, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9carbon atoms, where the aralkyl may be substituted by alkyl of 1 to 36carbon atoms.

Specific examples of the amine tungstates are those derived from PrimeneJM-T, tert-octadecylamine, tert-eicosylamine, 1-methyl-1-ethyl octadecylamine, 1,1-dimethyl octadecylamine, 1-methyl-1-butyl hexadecylamine,1-triacontylamine, oleyl amine, lauryl amine, and tall oil amine.

Polyamines are preferably represented by general formula

wherein R₇, R₈ and R₉ are each independently hydrogen; C₁ to C₂₅straight or branched chain alkyl radicals; C₁ to C₁₂ alkoxy-(C₆alkylene) radicals; C₂ to C₁₂ alkylamino-C₂ to C₆ alkylene) radicals;each s can be the same or a different number of from 1 to 6, preferably2 to 4; and t is a number from 0 to 10, preferably 2 to 7. At least oneof R₇, R₈ and R₉ must be hydrogen.

Suitable amines include: 1,2-diaminoethane; 1,3-diaminopropane;1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such asdiethylene triamine; triethylene tetramine; tetraethylene pentamine;polypropylene amines such as 1,2-propylene diamine;di-(1,2-propylene)triamine; di(1,3-propylene)-triamine;N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl)ethylene diamine;N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine;N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);diisopropanol amine; diethanol amine; triethanol amine; aminomorpholines such as N-(3-amino-propyl)morpholine; etc.

In order to improve solubility of the organotungsten product in baseoils and finished oils, it is useful for the mono-substituted diamine tohave a high hydrocarbon character. For example, the diamine can berepresented by the following general structure:

where x is 1 or 2, and R is a hydrocarbon-containing group containing aminimum of about 6 carbon atoms, and up to 24 carbon atoms. R can bealiphatic or aromatic. R, in addition to the minimum of about 6 carbonatoms, may also contain oxygen, but preferably R does not include sulfuror additional nitrogen. It is preferred that R contains a minimum of 10carbon atoms in order to further improve the organotungsten productsolubility in base oil. The most preferred R contains oxygen in additionto the carbons, such as where R is an alkyloxyalkylene group. Where Rrepresents an alkyloxyalkylene group, R can be represented by thestructure —X₁—O—X₂, where X₁ is an alkylene of 2, 3 or 4 carbons andpreferably is propylene or ethylene, and X₂ is an alkyl moiety having 3to 30 carbon atoms, more preferably an alkyl moiety having 7 to 20carbon atoms, and where X₂ can be a straight or branched, saturated orpartially unsaturated hydrocarbon chain.

Examples of some mono-substituted diamines that may be used includephenylaminopropylamine, hexylaminopropylamine, benzylaminopropylamine,octylaminopropylamine, octylaminoethylamine, dodecylaminopropylamine,dodecylaminoethylamine, hexadecylaminopropylamine,hexadecylaminoethylamine, octadecylaminopropylamine,octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane,octyloxypropyl-1,3-diaminopropane, decyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,dodecyloxypropyl-1,3-diaminopropane,tetradecyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,isododecyloxypropyl-1,3-diaminopropane, isotridecyloxypropyl-1,3-dia-minopropane. Mono-substituted diamines derived from fatty acids mayalso be used. Examples include N-coco alkyl-1,3-propanediamine (DuomeenC), N-tallow alkyl-1,3-propanediamine (Duomeen T), andN-oleyl-1,3-propanediamine (Duomeen OL), all obtained from Akzo Nobel.

Other useful amine compounds include alicyclic diamines such as1,4-di-(aminomethyl)cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, and N-aminoalkyl piperazines of the generalformula:

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3.

in which n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, or substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, aryl, aralkyl, cycloalkyl or heterocyclic radical, substitutedif desired with halogen, nitro groups, alkyl groups, alkoxy groups oramino groups, and, when m=1, T represents hydrogen. Salts of the abovestructures include carboxylic including aliphatic, aromatic and polycarboxylic, carbonic, sulfonic and phosphoric acid salts.

R^(a), R^(b), R^(c) are independently hydrogen, alkyl, alkenyl, oralkoxy of 1 to 36 carbons, cycloalkyl of 6 to 32 carbons, alkylamino of1 to 36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl,hydroxyalkyl, or hydroxycycloalkyl of 1 to 20 carbon atoms, methoxyalkylof 1 to 20 carbon atoms, aralkyl of 7 to 9 carbon atoms, where the arylgroup of the aralkyl is further substituted by alkyl of 1 to 36 carbonatoms. When m=2, T is alkylene of 1 to 12 carbons or arylene of 6 to 10carbons, or a plurality of radicals being able to be joined, containinghetero atoms also by hetero atoms such as O, N or S, if desired.

Preferred imidazoline structures are where R is a long chain alkyl up to18 carbon atoms, m=1 and R^(c) is one of 2-hydroxyethyl, or 2-aminoethylor 2-amido ethyl substituents.

Examples of such amines include 2-pentadecyl imidazoline, aminoethyloleyl imidazoline and N-(2-aminoethyl)piperazine.

2.0 Sulfur-Containing Organotungsten Compounds

The sulfur-containing organotungsten compounds of the invention may beprepared by a variety of methods. One method involves reacting a sulfurand phosphorus-free tungsten source with an amino group and one or moresulfur sources. Non-limiting examples of sulfur sources include carbondisulfide, hydrogen sulfide, sodium sulfide and elemental sulfur.Alternatively, the sulfur-containing tungsten compounds may be preparedby the reaction of a sulfur-free tungsten source with an amino group orthiuram group and optionally a second sulfur source. Examples of sulfur-and phosphorus-free tungsten sources include tungstic acid, tungstentrioxide, ammonium ortho tungstate, ammonium meta tungstate, ammoniumparatungstate, sodium tungstate, potassium tungstate and tungstenhalides. The amino groups may be monoamines, diamines, or polyamines. Asan example, the reaction of tungsten trioxide with a secondary amine andcarbon disulfide produces tungsten dithiocarbamates.

An alternate approach includes the reaction of sulfur- andphosphorus-free tungsten sources including tungstic acid, tungstentrioxide, ammonium ortho tungstate, ammonium meta tungstate, ammoniumparatungstate, sodium tungstate, and potassium tungstate with asulfurated amine precursor.

Examples of sulfur containing organotungsten compounds appearing inpatents and patent applications include the following all of which arehereby incorporation by reference in their entirety:

Compounds prepared by the reaction of divalent metal tungstates withdithiocarbamates in an alkaline sodium sulfide and/or sodium hydrogensulfide solution as described in WO 2004/043910 A2.

Compounds prepared by the reaction of a primary amine with a CS₂ or COS,and subsequent reaction of the dithiocarbamic acid produced with atungsten containing compound, as described in U.S. Pat. No. 4,846,983.

Sulfurized oxymetalorganophosphorodithioates, and sulfurized oxymetaldithiocarbamates as described in U.S. Pat. No. 4,529,526 wherein themetal is tungsten.

Tungsten dithiocarbamates are illustrated with the following structure,

where R⁶ and R⁷ are independently the same or different and are selectedfrom H and C₁ to C₃₀ and are an alkyl group, a cycloalkyl group, an arylgroup or an alkaryl group, with the proviso that at least one of R⁶ orR⁷ is H for at least one of the thiocarbamate groups, and at least oneof R⁶ or R⁷ is hydrocarbyl for each of the thiocarbamate groups, M is W,X is O or S, b₁ is at least 1, a₁ is at least 1 depending on theoxidation state of M, c₁ is at least 1 depending on the oxidation stateof M and d₁ is 0 or at least 1 depending on the oxidation state of M.Generally, a₁ and b₁ will range from 1 to about 5, c₁ will range from 1to about 6 and d₁ will be 0 or range from 2 to about 10. In a preferredembodiment, a₁ will be 1 or 2, b₁ will be 1 or 2, c₁ will be 1 or 2, andd₁ will be 0 or 2.

Sulfurized oxymetal organophosphorodithioates are illustrated with thefollowing structure.

wherein M is tungsten, R⁸ and R⁹ may be the same or different, each ofR⁸ and R⁹ contains from 1 to 30 carbon atoms and are selected from thegroup consisting of an alkyl group, a cycloalkyl group, an aryl group,and a alkylaryl group; and x₁ and y₁ are positive real numberssatisfying the equation: x₁+y₁=4.3. Silicon Containing Organotungsten Compounds

The silicon containing organotungsten compound of this invention may beprepared by a variety of methods. One method involves reacting a sulfurand phosphorus-free tungsten source with an amino silane. Examples ofsulfur- and phosphorus-free tungsten sources include tungstic acid,tungsten trioxide, ammonium ortho tungstate, ammonium meta tungstate,ammonium paratungstate, sodium tungstate and potassium tungstate.

Particularly useful are aminosilanes of the formula

in which R₁₇ and R₁₈ are independently hydrogen, C₁-C₂₅ alkyl,2-hydroxyethyl, C₃-C₂₅ alkyl which is interrupted by oxygen or sulfur;C₂-C₂₄ alkenyl or

R₁₉ is C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen orsulfur; hydroxyl, C₁-C₁₈ alkoxy or C₂-C₂₄ alkenyl, R₂₀ is hydroxyl,C₁-C₁₈ alkoxy or C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur;and, if a and b together are 1, three radicals R₂₀ together are N(CH₂CH₂O—)₃, X₃ is C₁-C₁₈ alkylene, C₂-C₂₀ alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈ cycloalkylene, phenylene or naphthylene which isunsubstituted or substituted by C₁-C₄ alkyl; or is C₄-C₁₈ alkylene whichis interrupted by oxygen, sulfur or

R₂₁ is hydrogen or C₁-C₈ alkyl with the proviso that two nitrogen atomsare not attached to the same carbon atom, a is 1 or 2, and b is 0, 1 or2.

Examples of amino silanes useful in this invention include, aminopropyltriethoxysilane, aminopropyl trimethoxy silane, aminopropyldiethoxysilane, aminopropyl methyldimethoxysilane, aminoethylaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropylmethyldiethoxysilane, aminoethyl aminomethyltriethoxysilane,aminoethyl aminomethylmethyldiethoxysilane,diethylenetriaminopropyltrimethoxysilane,diethylenetriaminopropyltriethoxysilane,diethylenetriaminopropylmethyldimethoxysilane,diethylenetriaminopropylmethyldiethoxysilane,diethylenetriaminomethyldimethoxysilane,cyclohexylaminopropyltrimethoxysilane,cyclohexylaminopropyltriethoxysilane,cyclohexylaminopropylmethyldimethoxysilane,cyclohexylaminopropylmethyldiethoxysilane,cyclohexylaminomethyltriethoxysilane,cyclohexylaminomethylmethyldiethoxysilane,hexanediaminomethyltriethoxysilane, phenylaminomethyltrimethoxysilane,phenylaminopropyltrimethoxysilane, phenylaminopropyltriethoxysilane,phenylaminopropyl methyldimethoxysilane, phenylaminopropylmethyldiethoxysilane, phenylaminomethylmethyldimethoxysilane,phenylaminomethylmethyldiethoxysilane, phenylaminomethyltriethoxysilane,diethylaminomethyltriethoxysilane, diethylaminomethyltrimethoxysilane,diethylaminopropyltrimethoxysilane, diethylaminopropylmethyldimethoxysilane, diethylaminopropyl methyldiethoxysilane,dimethylaminopropyl methyldiethoxysilane,(diethylaminomethyl)methyldiethoxysilane,methylaminopropyltrimethoxysilane, bis((3-triethoxysilyl)propyl)amine,piperazinylpropylmethyldimethoxysilane,piperazinylpropylmethyldiethoxysilane,piperazinylmethylmethyldiethoxysilane,morpholinylpropyltrimethoxysilane, morpholinylpropyltriethoxysilane,morpholinylpropylmethyldimethoxysilane,morpholinylpropylmethyldiethoxysilane, morpholinylmethyltriethoxysilane,morpholinylmethylmethyldiethoxysilane,diaminomethylmethyldiethoxysilane,dimethyldiaminopropylmethyldiethoxysilane,dimethyldiaminomethylmethyldiethoxysilane,aminohexylaminomethyltrimethoxysilane,aminohexylaminopropyltrimethoxysilane,octanoylaminopropyltriethoxysilane, methylaminopropyltrimethoxysilane,methylaminopropylmethyldiethoxysilane,methylaminomethylmethyldiethoxysilane,ethylaminopropylmethyldiethoxysilane, ethylaminomethylmethyldiethoxysilane.

Also useful are silicone amines commercially available from Siltechunder the Silamine tradename. The structures mentioned in the U.S. Pat.No. 5,378,787, which is hereby incorporation by reference in itsentirety, are also useful and are as follows:

where a and b are integers ranging from 0 to 2000.

4.0 Organoamine Tungstates with Ethoxylated Amines

The organoamine tungstate compounds useful in the present invention maybe prepared by a variety of methods. One method involves reacting asulfur and phosphorus-free tungsten source with an ethoxylated amine.Examples of sulfur- and phosphorus-free tungsten sources includetungstic acid, tungsten trioxide, ammonium ortho tungstate, ammoniummeta tungstate, ammonium paratungstate, sodium tungstate and potassiumtungstate.

Particularly useful ethoxylated fatty amines are

where Z is straight or branched chain alkyl of from about 8 to 26 carbonatoms, alkoxy alkyl of 4 to 22 carbon atoms, n=2 to about 50, andx₁=from about 1 to about 49.

Specific embodiments include, isopropyloxypropyl amine,isohexyloxypropyl amine, 2-ethylhexyloxypropyl amine, octyl/decyloxypropyl amine, isodecyloxypropyl amine, isododecyloxypropyl amine,dodecyl/tetradecyloxypropyl amine, isotridecyloxypropyl amine,tetradecyloxypropyl amine, linear alkoxypropyl amine,octadecyl/hexadecyloxypropyl amine, octyl/decyloxypropyl-1,3-diaminopropane, isodecyloxypropyl 1,3-diaminopropane,isododecyloxypropyl 1,3-diaminopropane, dodecyl/tetradecyloxypropyl1,3-diaminopropane, isotridecyloxypropyl 1,3-diaminopropane,tetradecyloxypropyl 1,3-diaminopropane,bis-(2-hydroxyethyl)isodecyloxypropyl amine,bis-(2-hydroxyethyl)isotridecyloxypropyl amine, bis-(2-hydroxyethyl)linear alkoxypropyl amine, bis-(2-hydroxyethyl)soya amine,bis-(2-hydroxyethyl)tallow amine, poly(5)oxyethylene isodecyloxypropylamine, poly(5)oxyethylene isotridecyloxypropyl amine, N-tallow-poly(3)oxyethlene-1,3-diaminopropane, isodecyloxypropylbis-(2-hydroxyethyl)methyl ammonium chloride, isotridecyloxypropylbis-(2-hydroxyethyl)methyl ammonium chloride, octadecylbis-(2-hydroxyethyl)methyl ammonium chloride, isotridecyloxypropylpoly(5)oxyethylene methyl ammonium chloride, monosoya methyl ammoniumchloride, tallow diamine diquaternary coco poly(15) oxyethylene methylammonium chloride and trimethyl stearyl ammonium chloride.

5. Organoamine Tungstates with Alkylated Phenothiazine

The organoamine tungstate compounds useful in the present invention maybe prepared by a variety of methods. One method involves reacting asulfur and phosphorus-free tungsten source with an alkylatedphenothiazine. Examples of sulfur- and phosphorus-free tungsten sourcesinclude tungstic acid, tungsten trioxide, ammonium ortho tungstate,ammonium meta tungstate, ammonium paratungstate, sodium tungstate andpotassium tungstate.

An alkylated phenothiazine suitable for this invention must be oilsoluble or dispersible and correspond to the general formula below wherethe substituents R₁₁—R₁₄ could contain heteroatoms,

R₁₁ and R₁₂ are hydrogen or together can form a fused six-memberaromatic ring.

One of R₁₃ and R₁₄ is hydrogen and the other is C₂-C₃₀ alkyl,cyclo-C₅-C₁₂ alkyl, —C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl orα,α-dimethylbenzyl; or both R₁₃ and R₁₄ are C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ hydrogen; or R₁₃ is hydrogen and R₁₄ is C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ together form a fused six-member aromatic ring.

R₁₅ is hydrogen, C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or agroup —CH₂SR₄, where R₄ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or analkylene, aralkylene bridging two phenothiazine moieties.

Typical examples of alkylphenothiazine include but are not limited tomonotetradecylphenothiazine, ditetradecylphenothiazine,monodecylphenothiazine, didecylphenothiazine monononylphenothiazine,dinonylphenothiazine, monoctylphenothiazine and dioctylphenothiazine.

6. Organoamine Tungstates with Alkylated Diarylamine

The organoamine tungstate compounds useful in the present invention maybe prepared by a variety of methods. One method involves reacting asulfur and phosphorus-free tungsten source with an alkylateddiarylamine. Examples of sulfur- and phosphorus-free tungsten sourcesinclude tungstic acid, tungsten trioxide, ammonium ortho tungstate,ammonium meta tungstate, ammonium paratungstate, sodium tungstate andpotassium tungstate.

The diarylamines that may optionally be used and that have been found tobe useful in this invention are well known antioxidants and there is noknown restriction on the type of diarylamine that can be used.Preferably, the diarylamine has the formula:

Wherein R₂₂ and R₂₃ each independently represents a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms. Illustrativeof substituents for the aryl group include aliphatic hydrocarbon groupssuch as alkyls having from 1 to 30 carbon atoms, hydroxy groups, halogenradicals, carboxylic acid or ester groups, or nitro groups. The aryl ispreferably substituted or unsubstituted phenyl or naphthyl, particularlywherein one or both of the aryl groups are substituted with at least onealkyl having from 4 to 30 carbon atoms, preferably from 4 to 18 carbonatoms, most preferably from 4 to 12 carbon atoms. It is preferred thatone or both aryl groups be substituted, e.g. mono-alkylateddiphenylamine, di-alkylated diphenylamine, or mixtures of mono- anddi-alkylated diphenylamines.

R₂₄ is hydrogen, C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or agroup —CH₂SR₅, where R₅ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or analkylene, aralkylene bridging two amine moieties.

The diarylamines used in this invention can be of a structure other thanthat shown in the above formula that shows but one nitrogen atom in themolecule. Thus the diarylamine can be of a different structure providedthat at least one nitrogen has 2 aryl groups attached thereto, e.g. asin the case of various diamines having a secondary nitrogen atom as wellas two aryl groups bonded to one of the nitrogen atoms.

The diarylamines used in this invention should be soluble in theformulated crankcase oil package. Examples of some diarylamines that maybe used in this invention include diphenylamine; alkylateddiphenylamines; 3-hydroxydiphenylamine; N-phenyl-1,2-phenylenediamine;N-phenyl-1,4-phenylenediamine; monobutyldiphenylamine;dibutyldiphenylamine; monooctyldiphenylamine; dioctyldiphenylamine;monononyldiphenylamine; dinonyldiphenylamine;monotetradecyldiphenylamine; ditetradecyldiphenylamine;phenyl-alpha-naphthylamine; monooctyl phenyl-alpha-naphthylamine;phenyl-beta-naphthylamine; monoheptyldiphenylamine;diheptyldiphenylamine; p-oriented styrenated diphenylamine; mixedbutyloctyldiphenylamine; and mixed octylstryryldiphenylamine, andmixtures thereof. Examples of commercial diarylamines include, forexample, IRGANOX™ L06, IRGANOX™ L57 (mixed butyloctyl diphenyl amine)and I IRGANOX™ L67 from Ciba Specialty Chemicals; NAUGALUBE™ AMS,NAUGALUBE™ 438, NAUGALUBE™ 438R, NAUGALUBE™ 438L, NAUGALUBE™ 500,NAUGALUBE™ 640, NAUGALUBE™ 680, and NAUGARD PANA™ from CromptonCorporation; GOODRITE™ 3123, GOODRITE™ 3190X36, GOODRITE™ 3127,GOODRITE™ 3128, GOODRITE™ 3185X1, GOODRITE™ 3190X29, GOODRITE™ 3190X40,GOODRITE™ 3191 and GOODRITE™ 3192 from Noveon Specialty Chemicals;VANLUBE™ DND, VANLUBE™ NA, VANLUBE™ PNA, VANLUBE™ SL (mixed octylstyryldiphenylamine), VANLUBE™ SLUP, VANLUBE™ SS, VANLUBE™ 81, VANLUBE™ 848,and VANLUBE™ 849, VANLUBE™ 961 (mixed butyloctyl diphenyl amine) from R.T. Vanderbilt Company Inc, LUBRIZOL™ 5150A & C from LUBRIZOL™, andNA-LUBE™ AO-140 (mixed butyloctyl diphenyl amine), NA-LUBE™ AO-150(mixed octylstyryl diphenylamine), from King Industries.

7. Organoamine Tungstates with Amines Containing Other StabilizingMoieties

The organoamine tungstate compounds useful in the present invention maybe prepared by a variety of methods. One method involves reacting asulfur and phosphorus-free tungsten source with an alkylated triazole,or a phenolic antioxidant. Examples of sulfur- and phosphorus-freetungsten sources include tungstic acid, tungsten trioxide, ammoniumortho tungstate, ammonium meta tungstate, ammonium paratungstate, sodiumtungstate and potassium tungstate.

A triazole having the formula

wherein R₂₅ is hydrogen or a C₁-C₂₀ alkyl residue; R₂₆ and R₂₇ are thesame or different and each is H, C₁-C₂₀ alkyl, C₃-C₂₀ alkenyl, C₅-C₁₂cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆ and R₂₇, together withthe nitrogen atom to which they are attached, form a 5-, 6- or7-membered heterocyclic residue or R₂₆ and R₂₇ is each a residue offormula:R₂₈X₃[(alkylene)O]n ₁(alkylene)-wherein X₃ is O, S or N(R₂₈), R₂₈ is hydrogen or C₁-C₂₀ alkyl,“alkylene” is a C₁-C₁₂ alkylene residue and n₁ is an integer from 0 to6;

R₃₀ is hydrogen, C₁-C₂₀ alkyl or C₆-C₁₀ aryl or C₇-C₁₈ alkyl phenyl; andR₃₁ is hydrogen, C₁-C₂₀ alkyl or a residue —CH₂ NR₂₆R₂₇ wherein R₂₆ andR₂₇ have their previous significance or

R₂₆ has its previous significance and R₂₇ is a residue of formula

or R₂₇ is a residue of formula as defined above and R₂₆ is a residue offormula-[alkylene]n ₁-N(R₃₂)_A₋[N(R₃₂)₂ ]m ₁)in which m₁ is 0 or 1, and when m₁ is 0, A is a residue of formula (I,)and when m₁ is 1, A is alkylene or C₆-C₁₀ arylene, and alkylene and n₁have their previous significance and R₃₂ is a residue of formula I, asdefined above.

A substituted phenol of the formula

wherein, R₄₂, are independently alkyl of 1 to 18 carbon atoms,cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alkylof 1 to 18 carbon atoms, aralkyl of 7 to 9 carbon atoms or said aralkylsubstituted by alkyl of 1 to 18 carbon atoms. R₂₆ and R₂₇ are the sameor different and each is H, C₁-C₂₀ alkyl, C₃-C₂₀ alkenyl, C₅-C₁₂cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆ and R₂₇, together withthe nitrogen atom to which they are attached, form a 5-, 6- or7-membered heterocyclic residue or R₂₆ and R₂₇ is each a residue offormula:R₂₈X₃[(alkylene)O]n ₁(alkylene)-)wherein X₃ is O, S or N(R₂₈), R₂₈ is hydrogen or C₁-C₂₀ alkyl,“alkylene” is a C₁-C₁₂ alkylene residue and n₁ is 0 or an integer from 1to 6.8.0 Organoamine Tungstates from Polyamine Salts

The organoamine tungstate compounds useful in the present invention maybe prepared by a variety of methods. One method involves reacting asulfur and phosphorus-free tungsten source with an amine, carboxylate,sulfonate, dithiophosphate, naphthenates, phosphonates, phenoxyalkanoates, and N-acyl sarcosinates. Examples of sulfur- andphosphorus-free tungsten sources include tungstic acid, tungstentrioxide, ammonium ortho tungstate, ammonium meta tungstate, ammoniumparatungstate, sodium tungstate and potassium tungstate.

A soluble acid salt of a carboxylic acid, a mono or disulfonic acid,naphthenic acid, dithiophosphoric acid or alkyl phosphonic acid with apolyamine is prepared in the first step and subsequently reacted withvarious tungsten sources as outlined above to the desired tungstate,which are oil soluble

In certain embodiments, long-chain monocarboxylic acids suitable for usein the present invention preferably contain at least 8, and morepreferably at least 12, and up to 100 carbon atoms. In preferredembodiments, examples of suitable acids for use in the present inventioninclude fatty acids such as coconut acid, hydrogenated coconut acid,menhaden acid, hydrogenated menhaden acid, tallow acid, hydrogenatedtallow acid, and soya acid. Additional long-chain carboxylic acids thatmay be used include lauric acid, myristic acid, palmitic acid, stearicacid, isostearic acid, arachidic acid, behenic acid, erucic acid, oleicacid, linoleic acid, and linolenic acid. Mixtures of acids may also beused and are sometimes preferred. For example, commercial oleic acid isactually a mixture of many fatty acids ranging in carbon chain lengthfrom 14 to 20.

The sulfonic acid of the current invention could be one of thefollowing:

1) An alkylated aryl sulfonic acid selected from the group consisting of

wherein R¹⁰ is H or an alkyl group containing up to 20 carbon atoms, andx is an integer from 0 to 2.

An alkylated aryl sulfonic acid selected from the group consisting of

wherein R₅₁, R₅₂, R₅₃ and R₅₄ are individually selected from the groupconsisting of hydrogen or essentially linear hydrocarbyl groups havingabout 9 to about 22 carbon atoms; and wherein l, m, n and p are integersfrom 0 to 4 and the sum of l+m+n+p is at least 1; and wherein R₅₁, R₅₂,R₅₃ and R₅₄ is a hydrogen where either l, m, n, or p is 0.

2) An alkylated aryl disulfonic acid selected from the group consistingof

and structure II

wherein each of R¹¹ and R¹² is the same or different and is a linear orbranched alkyl group with 6 to 16 carbons, y is 0 to 3, z is 0 to 3 withthe proviso that y+z is 1 to 4, n is 0 to 3, B is a divalent moietyselected from the group consisting of —C(R¹³)(R¹⁴)—, wherein each of R¹³and R¹⁴ is H or independently a linear or branched alkyl group of 1-4carbons and n is 1; —C(═O)—, wherein n is 1; —O— wherein n is 1; —S—,wherein n is 1 to 3; and —SO₂—, wherein n is 1;

Suitable sulfonic acids include alkane sulfonic acid, aralkyl sulfonicacid, including dodecyl benzene sulfonic acid, didodecyl benzenesulfonicacid, and sulfonic acids derived from various hydrocarbon feedstock.Examples of other suitable sulfonic acids include mono-, di-, andpoly-alkylated naphthalenesulfonic acids, e.g., dinonyl napthalenesulfonic acid, didodecyl naphthalene sulfonic acids, diphenyl ethersulfonic acid, napthalene disulfide sulfonic acid, dicetyl thianthrenesulfonic acid, dialauryl betanaphthol sulfonic acid, dicaprylnitronaphthalene sulfonic acid, unsaturated paraffin wax sulfonic acid,hydroxy substituted paraffin wax sulfonic acid, tetraamylene sulfonicacid, mono- and poly-chloro substituted paraffin wax sulfonic acid,nitrosoparaffin wax sulfonic acid, cycloaliphatic sulfonic acid such aslauryl-cyclohexyl sulfonic acid, mono- and poly-wax-substitutedcyclohexyl sulfonic acid, and the like. Suitable acid components includenaphthenic acid, which encompasses a mixture of monobasic acids ofcycloparaffins which are derived from either cyclopentane or cyclohexaneand cyclopentane and a great variety of homologs and higher molecularweight analogs. Conventionally, the acids of commercial mixtures ofnaphthenic acids have molecular weights in the range of from about 180to 350. Suitable acid components include dihydrocarbylphosphoric acids,dihydrocarbyldithiophosphoric acids, and dihydrocarbylmonothiophosphoricacids, from the following

wherein Y₁ and Y₂ are each independently of the other S or O R¹⁵ and R¹⁶are each independently of the other H, C₃-C₁₈ alkyl, C₅-C₁₂ cycloalkyl,C₅-C₆ cycloalkylmethyl, C₉-C₁₀ bicycloalkylmethyl, C₉-C₁₀tricycloalkylmethyl, phenyl, C₇-C₂₄-alkylphenyl, or R¹⁵ and R¹⁶ togetherare the group of the partial formula:

R¹⁵ and R¹⁶ defined as C₉-C₁₀ bicycloalkylmethyl are typicallydecalinylmethyl. R¹⁵ and R¹⁶ defined as C₉-C₁₀ tricycloalkylmethyl arepreferably a group of formula:

R¹⁵ and R¹⁶ are preferably i-propyl, i-butyl, 2-ethylhexyl, octyl phenylor oleyl. Suitable acid components also include an alkyl phenoxyalkanoicacid of the formula

wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

Suitable acid components also include an N-acyl sarcosine derivative ofthe formula

wherein the acyl group R^(t)—C(═O)— is the residue of a fatty acidhaving 10 to 20 carbon atoms.

The polyamine compounds which may be employed in the production of theoil-soluble tungstate can be any suitable polyamine compound. In orderto improve solubility of the organo tungstate product in base oils andfinished oils, it is important for the mono-substituted diamine to havea high hydrocarbon character. For example, the diamine can berepresented by the following general structure:

where x is 1 or 2, and R is a hydrocarbon-containing group containing aminimum of about 6 carbon atoms and up to 24 carbon atoms. R can bealiphatic or aromatic. R, in addition to the minimum of about 6 carbonatoms, may also contain oxygen, but preferably R does not include sulfuror additional nitrogen. It is preferred that R contains a minimum of 10carbon atoms in order to further improve the organotungsten productsolubility in base oil. The most preferred R contains oxygen in additionto the carbons, such as where R is an alkyloxyalkylene group. Where Rrepresents an alkyloxyalkylene group, R can be represented by thestructure —X₁—O—X₂, where X₁ is an alkylene of 2, 3 or 4 carbons andpreferably is propylene or ethylene, and X₂ is an alkyl moiety having 3to 30 carbon atoms, more preferably an alkyl moiety having 7 to 20carbon atoms, and where X 2 can be a straight or branched, saturated orpartially unsaturated hydrocarbon chain. The use of a diamine includingan R group represented by —X₁—O—X₂ as defined herein in the reactionprocess makes it possible to maximize the level of tungstenincorporation levels in the oil soluble reaction product whileperforming the process without the use of volatile organic processingsolvents.

Examples of some mono-substituted diamines that may be used includephenylaminopropylamine, hexylaminopropylamine, benzylaminopropylamine,octylaminopropylamine, octylaminoethylamine, dodecylaminopropylamine,dodecylaminoethylamine, hexadecylaminopropylamine,hexadecylaminoethylamine, octadecylaminopropylamine,octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane,octyloxypropyl-1,3-diaminopropane, decyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,dodecyloxypropyl-1,3-diaminopropane,tetradecyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,isododecyloxypropyl-1,3-diaminopropane,isotridecyloxypropyl-1,3-dia-minopropane. Mono-substituted diaminesderived from fatty acids may also be used. Examples include N-cocoalkyl-1,3-propanediamine (Duomeen C), N-tallow alkyl-1,3-propanediamine(Duomeen T), and N-oleyl-1,3-propanediamine (Duomeen OL), all obtainedfrom Akzo Nobel.

Especially preferred polyamine compounds include diamine1,3-diaminopropane having an alkyl moiety selected from the groupconsisting of N-coco, N-tallow, N-soya and N-oleyl. The compound1,3-diaminopropane can be represented by the general formulaR—NH(C₃H₆NH₂) wherein R is an alkyl group representing the coco, tallow,soya or oleyl moiety.

Other suitable polyamines include tetraethylene pentamine and similarpolyamine types containing primary and/or secondary amine groups.Further suitable polyamines can be represented by the general formulasR(NH₂)₂ and R NH—(C₃H₆NH₂)₂ wherein R is an alkyl radical derived fromthe dimerization of a C₁₈ unsaturated fatty acid. Another group ofsuitable polyamine compounds can be represented by the general formulaR—N—(C₃H₆NH₂)₂ wherein R is an alkyl radical derived from tallow, oleyland lauryl fatty acids.Other useful amine compounds include alicyclic diamines such as1,4-di-(aminomethyl)cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, and N-aminoalkyl piperazines of the generalformula:

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3.

in which n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, or substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, aryl, aralkyl, cycloalkyl or heterocyclic radical, substitutedif desired with halogen, nitro groups, alkyl groups, alkoxy groups oramino groups, and, when m=1, represents also hydrogen. Salts of theabove structures include carboxylic including aliphatic, aromatic andpoly carboxylic, carbonic, sulfonic and phosphoric acid salts.R^(a), R^(b), R^(c) are independently hydrogen, alkyl, alkenyl or alkoxyof 1 to 36 carbons, cycloalkyl of 6 to 32 carbons or alkylamino of 1 to36 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenyl,hydroxyalkyl or hydroxycycloalkyl of 1 to 20 carbon atoms, methoxyalkylof 1 to 20 carbon atoms, aralkyl of 7 to 9 carbon atoms, where the arylgroup of the aralkyl group is further substituted by alkyl of 1 to 36carbon atoms.When m=2, T is alkylene of 1 to 12 carbons or arylene of 6 to 10carbons, or a plurality of radicals being able to be joined, containinghetero atoms also by hetero atoms such as O, N or S, if desired.Preferred imidazoline structures are where R is a long chain alkyl up to18 carbon atoms, m=1 and R^(c) is one of 2-hydroxyethyl, or 2-aminoethylor 2-amido ethyl substituents.Examples of such amines include 2-pentadecyl imidazoline, aminoethyloleyl imidazoline and N-(2-aminoethyl)piperazine.

Ammonium molybdates derived from these precursor salts that are acomponent of the present invention may also be prepared from amolybdenum source. The process for preparing the organoammoniummolybdates of the invention involves the use of one of severalmolybdenum sources including molybdenum trioxide, ammonium paramolybdateor ammonium heptamolybdate. A preferred molybdenum source is molybdenumtrioxide. The use of molybdenum trioxide results in effective molybdenumincorporation into the organic ligand made by the aforementioned firstprocess step, and it produces a reaction mass by the completion of thesecond step that does not require filtration.

9.0 Organoammonium Tungstates from the Reaction Product of MonoCarboxylic Acid with Diamines, Fatty Oil with Diamines and Naphthenyl,Alkylphenoxyalkanoyl and N-Sarcosoyl Polyamines.

The organoamine tungstate compounds useful in the present invention maybe prepared by a variety of methods. One method involves reacting asulfur and phosphorus-free tungsten source with the reaction product ofa mono carboxylic acid, fatty oil, vegetable oil, triglyceride orglycerol esters of fatty acids, naphthenic acid, alkylphenoxy alkanoicacid or N-acyl sarcosine with a monosubstituted alkylene diamine.Examples of sulfur- and phosphorus-free tungsten sources includetungstic acid, tungsten trioxide, ammonium ortho tungstate, ammoniummeta tungstate, ammonium paratungstate, sodium tungstate and potassiumtungstate.

In certain embodiments, examples of long-chain monocarboxylic acidssuitable for use in the present invention preferably contain at least 8,and more preferably at least 12, and up to 100 carbon atoms. Inpreferred embodiments, examples of suitable acids for use in the presentinvention include fatty acids such as coconut acid, hydrogenated coconutacid, menhaden acid, hydrogenated menhaden acid, tallow acid,hydrogenated tallow acid, and soya acid. Additional long-chaincarboxylic acids that may be used include lauric acid, myristic acid,palmitic acid, stearic acid, isostearic acid, arachidic acid, behenicacid, erucic acid, oleic acid, linoleic acid, and linolenic acid.Mixtures of acids may also be used and are sometimes preferred. Forexample, commercial oleic acid is actually a mixture of many fatty acidsranging in carbon chain length from 14 to 20.

Examples of preferred fatty or vegetable oils that may be used in theprocess of the present invention include groundnut oil, coconut oil,linseed oil, palm kernel oil, olive oil, cottonseed oil, grapeseed oil,corn oil, canola oil, palm oil, peanut oil, safflower seed oil, sesameseed oil, caster oil, rapeseed oil (low or high erucic acids), soyabeanoil, sunflower oil, herring oil, sardine oil, lard, menhaden oil, hazelnut oil, walnut oil, and tallow, and mixtures thereof. These fatty orvegetable oils can include those compounds generally known astriglycerides, which have the general structure as shown below

where R′, R″, or R′″ independently represent saturated or unsaturatedaliphatic hydrocarbon groups having from about 8 to about 22 carbonatoms, and preferably are hydrocarbon chains having about 12 to about 22carbon atoms. Mono- and diglycerides, either separately or in mixtureswith one or more triglycerides, are also useful as fatty or vegetableoils in the present invention, in which the R′, R″, or R′″ groupspresent have the same above meaning.

Suitable acid components include naphthenic acid, which encompasses amixture of monobasic acids of cycloparaffins which are derived fromeither cyclopentane or cyclohexane and cyclopentane and a great varietyof homologs and higher molecular weight analogs. Conventionally, theacids of commercial mixtures of naphthenic acids have molecular weightsin the range of from about 180 to 350.

Suitable acid components also include an alkyl phenoxyalkanoic acid ofthe formula

wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

Suitable acid components also include an N-acyl sarcosine derivative ofthe formula

wherein the acyl group R^(t)—C(═O)— is the residue of a fatty acidhaving 10 to 20 carbon atoms.

The polyamine compounds which may be employed in the production of theoil-soluble sulfonate tungstate can be any suitable polyamine compound.In order to improve solubility of the organo tungstate product in baseoils and finished oils, it is important for the mono-substituted diamineto have a high hydrocarbon character. For example, the diamine can berepresented by the following general structure:

where x is 1 or 2, and R is a hydrocarbon-containing group containing aminimum of about 6 carbon atoms and up to 24 carbon atoms. R can bealiphatic or aromatic. R, in addition to the minimum of about 6 carbonatoms, may also contain oxygen, but preferably R does not include sulfuror additional nitrogen. It is preferred that R contains a minimum of 10carbon atoms in order to further improve the organotungsten productsolubility in base oil. The most preferred R contains oxygen in additionto the carbons, such as where R is an alkyloxyalkylene group. Where Rrepresents an alkyloxyalkylene group, R can be represented by thestructure —X₁—O—X₂, where X₁ is an alkylene of 2, 3 or 4 carbons andpreferably is propylene or ethylene, and X₂ is an alkyl moiety having 3to 30 carbon atoms, more preferably an alkyl moiety having 7 to 20carbon atoms, and where X 2 can be a straight or branched, saturated orpartially unsaturated hydrocarbon chain. The use of a diamine includingan R group represented by —X₁—O—X₂ as defined herein in the reactionprocess makes it possible to maximize the level of tungstenincorporation levels in the oil soluble reaction product whileperforming the process without the use of volatile organic processingsolvents.

Examples of some mono-substituted diamines that may be used includephenylaminopropylamine, hexylaminopropylamine, benzylaminopropylamine,octylaminopropylamine, octylaminoethylamine, dodecylaminopropylamine,dodecylaminoethylamine, hexadecylaminopropylamine,hexadecylaminoethylamine, octadecylaminopropylamine,octadecylaminoethylamine, isopropyloxypropyl-1,3-diaminopropane,octyloxypropyl-1,3-diaminopropane, decyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,dodecyloxypropyl-1,3-diaminopropane,tetradecyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,isododecyloxypropyl-1,3-diaminopropane,isotridecyloxypropyl-1,3-diaminopropane. Mono-substituted diaminesderived from fatty acids may also be used. Examples include N-cocoalkyl-1,3-propanediamine (Duomeen C), N-tallow alkyl-1,3-propanediamine(Duomeen T), and N-oleyl-1,3-propanediamine (Duomeen OL), all obtainedfrom Akzo Nobel. Especially preferred are polyamine compounds includingdiamine 1,3-diaminopropane having an alkyl moiety selected from thegroup consisting of N-coco, N-tallow, N-soya and N-oleyl. The compound1,3-diaminopropane can be represented by the general formulaR—NH(C₃H₆NH₂) wherein R is an alkyl group representing the coco, tallow,soya or oleyl moiety.

Other suitable polyamines include tetraethylene pentamine and similarpolyamine types containing primary and/or secondary amine groups.Further suitable polyamines can be represented by the general formulasR(NH₂)₂ and R NH—(C₃H₆NH₂)₂ wherein R is an alkyl radical derived fromthe dimerization of a C₁₈ unsaturated fatty acid. Another group ofsuitable polyamine compounds can be represented by the general formulaR—N—(C₃H₆NH₂)₂ wherein R is an alkyl radical derived from tallow, oleyland lauryl fatty acids.

10.0 Organoammonium Tungstates from the Reaction Product of SubstitutedSuccinic Anhydrides with Polyamines

The organoamine tungstate compounds useful in the present invention maybe prepared by a variety of methods. One method involves reacting asulfur and phosphorus-free tungsten source with the reaction product ofsubstituted succinic anhydrides with polyamines. Examples of sulfur- andphosphorus-free tungsten sources include tungstic acid, tungstentrioxide, ammonium ortho tungstate, ammonium meta tungstate, ammoniumparatungstate, sodium tungstate and potassium tungstate.

Succinimides of the current invention may be represented by thefollowing general formula.

where R¹⁸ is a C6 to C30 isomerized alkenyl group, represented by:

(where g and h are integers whose sum is from 1 to 25), or its fullysaturated alkyl analog, R¹⁷ is an alkyl group, aryl group, containingone or more nitrogen atom and other heteroatoms.The succinimides of the present invention are those produced fromsuccinic anhydrides substituted with isomerized alkenyl groups or theirfully saturated alkyl analogs. Preparation of isomerized alkenylsuccinic anhydrides is described in, for example, U.S. Pat. No.3,382,172, hereby incorporated by reference in its entirety.Often these materials are prepared by heating alpha-olefins with acidiccatalysts to migrate the double bond to form an internal olefin. Thismixture of olefins (2-enes, 3-enes, etc.) is then thermally reacted withmaleic anhydride.

Typically olefins from C₆ (e.g. 1-hexene) to C₃₀ (e.g. 1-tricosane) areused. Suitable isomerized alkenyl succinic anhydrides of structure (1)

include isodecylsuccinic anhydride (x+y=5), iso-dodecyisuccinicanhydride (x+y=7), iso-tetradecylsuccinic anhydride (x+y=9),iso-hexadecylsuccinic anhydride (x+y=11), iso-octadecylsuccinicanhydride (x+y=13) and isoeicosylsuccinic anhydride (x+y=15). Preferredmaterials are isohexadecylsuccinic anhydride and iso-octadecylsuccinicanhydride.

The materials produced by this process contain one double bond (alkenylgroup) in the alkyl chain. The alkenyl substituted succinic anhydridesmay be easily converted to their saturated alkyl analogs byhydrogenation.

Suitable primary and secondary amines useful to produce the succinimidesare represented by structure

where R²⁵, R²⁶, and R²⁷ are independently selected from the groupconsisting of H, C₁ to C₂₅ straight or branched chain alkyl radicals, C₁to C₁₂ alkoxy radicals; C₂ to C₆ alkylene radicals; u is an integer from1 to 6, preferably 2 to 4; and v is an integer from 0 to 10, preferablyfrom 1 to 4.

Bis succinimides of the current invention may be represented by thefollowing general formula

wherein, R²¹ and R²² may be identical or different from each other andare each hydrocarbon groups having 5 or more carbons; R²³ is a divalenthydrocarbon group having 1 to 5 carbons; R²⁴ is a hydrogen atom or ahydrocarbon group having 1 to 20 carbons; and n is an integer in therange of 0 to 10. In the above general formula, R²¹ and R²² may be thesame as each other or different from each other, and are each saturatedor unsaturated hydrocarbon groups having 5 or more carbons, preferably 5to 40 carbons. Examples of hydrocarbon groups include pentyl groups,hexyl groups, heptyl groups, octyl groups, nonyl groups, decyl groups,dodecyl groups, tridecyl groups, tetradecyl groups, pentadecyl groups,hexadecyl groups, heptadecyl groups, octadecyl groups, nonadecyl groups,oleyl groups and other hydrocarbon groups having up to 40 carbons.Preferred hydrocarbon groups include straight chain hydrocarbon groupshaving between 8 and 25 carbons. In the above general formula, R²³ is adivalent hydrocarbon group having 1 to 5 carbons, preferably an alkylenegroup having 2 or 3 carbons.

In the above general formula, R²⁴ is a hydrogen atom or a hydrocarbongroup having 1 to 20 carbons. Examples of hydrocarbon groups includealkyl groups having 1 to 20 carbons; alkenyl groups having 2 to 20carbons; cycloalkyl groups having 6 to 20 carbons; and aryl groupshaving 6 to 20 carbons. The aryl groups may have an alkyl group having 1to 12 carbons. Hydrogen atoms and alkyl groups having 1 to 10 carbonsare particularly preferred as R²⁴. Groups having a number of (i.e. 1 to5 of each) amino groups and/or amide bonds in their structure can beused as the above-described hydrocarbon groups.

The amino groups are represented by —NH— or —NH₂; and the amide bondsare represented by

They may be bonded with the carbons of the hydrocarbon group at anarbitrary position.

The bis succinimides of the present invention are those produced fromsuccinic anhydrides substituted with isomerized alkenyl groups or theirfully saturated alkyl analogs, and polyamines. Suitable polyamines aresaturated amines of the general formula:

where R²⁵, R²⁶, and R²⁷ are independently selected from the groupconsisting of H, C₁ to C₂₅ straight or branched chain alkyl radicals, C₁to C₁₂ alkoxy radicals; C₂ to C₆ alkylene radicals; u is an integer from1 to 6, preferably 2 to 4; and v is an integer from 0 to 10, preferablyfrom 1 to 4.

Non-limiting examples of suitable polyamine compounds include:1,6-diaminohexane, diethylene triamine, triethylene tetramine,tetraethylene pentamine, and pentaethylene hexamine. Useful mixtures ofpolyamines having from 5 to 7 nitrogen atoms per molecule are availablefrom Dow Chemical Co. as Polyamine H, Polyamine 400 and Polyamine E-300.

Polyoxyalkylene amines are also useful in this invention and are shownas structureH₂N-alkylene-(-O-alkylene-)u ₁-NH₂where u₁ is an integer of from 1 to 10. The polyamines have molecularweights from about 100 to 500. The preferred polyoxyalkylene polyaminesinclude polyoxyethylene and polyoxypropylene diamines and thepolyoxypropylene triamines. Commercial polyoxyalkylene amines areavailable from Jefferson Chemical Co. sold under the trade name“Jeffamines D-230, D-400, D-1000, T-430,” etc.

Organo ammonium molybdates derived from these precursor succinimidesaccording to the invention may also be prepared from one of variousmolybdenum sources. The process for preparing the organoammoniummolybdates of the invention involves the use of one of severalmolybdenum sources including molybdenum trioxide, ammonium paramolybdateor ammonium heptamolybdate. A preferred molybdenum source is molybdenumtrioxide. The use of molybdenum trioxide results in effective molybdenumincorporation into the organic ligand made by the aforementioned firstprocess step, and it produces a reaction mass by the completion of thesecond step that does not require filtration. There is no particularrestriction on the type of secondary diarylamine used in the inventionas an antioxidant. Preferably, the secondary diarylamine antioxidant hasthe general formula:

wherein R₂₂ and R₂₃ each independently represents a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms. Illustrativeof substituents for the aryl include aliphatic hydrocarbon groups suchas alkyl having from about 1 to 20 carbon atoms, hydroxy, carboxyl ornitro, e.g., an alkaryl group having from 7 to 20 carbon atoms in thealkyl group. The aryl is preferably substituted or unsubstituted phenylor naphthyl, particularly wherein one or both of the aryl groups aresubstituted with an alkyl such as one having from 4 to 30 carbon atoms,preferably from 4 to 18 carbon atoms, most preferably from 4 to 9 carbonatoms. It is further preferred that one or both aryl groups besubstituted, e.g. mono alkylated diphenylamine, dialkylateddiphenylamine, or mixtures of mono- and di-alkylated diphenylamines.

The secondary diarylamines used in this invention can be of a structureother than that shown in the above formula which shows but one nitrogenatom in the molecule. Thus, the secondary diarylamine can be of adifferent structure provided that at least one nitrogen has 2 arylgroups attached thereto, e.g., as in the case of various diamines havinga secondary nitrogen atom as well as two aryls on one of the nitrogens.The secondary diarylamines used in this invention preferably haveantioxidant properties in lubricating oils, even in the absence of thetungsten compound.

It is preferred that the oil-soluble secondary aromatic amines arediphenylamines of general formula:

wherein D₁ and D₂ may be the same or different and each independentlyrepresents a hydrocarbyl radical as hereinbefore defined. It ispreferred that D₁ and D₂ are C₁ to C₂₈ aliphatic hydrocarbyl radicals. Eand F may be the same or different and may equal 0, 1, 2 or 3. It ispreferred that E and F are the same and that they equal 1. It is alsopreferred that the diphenylamines have a nitrogen content of between 2.5and 5% by weight. It is preferred that D₁ and D₂ are located in the metaor para positions relative to the amino substitution in the aromaticrings of the diphenylamines. Examples of suitable diphenylamines includedi-octyldiphenylamine, t-pentyldiphenylamine, diisobornyldiphenylamine,didecyldiphenylamine, didodecyldiphenylamine, dihexyldiphenylamine,di-t-butyidiphenylamine, di-t-octyldiphenylamine, dinonylamine,dibutyldiphenylamine, distyryldiphenylamine. Other suitablediphenylamines include di-substituted derivatives wherein the D₁ and D₂are different and independently represent hydrocarbyl radicals, such ast-butyl, t-octyl, styryl, n-butyl or n-octyl for example. Some of thesediphenylamines are commercially available and are sold under thetrademarks, VANLUBE™ DND, NAUGALUBE™ 438L, PEARSALL™ OA502, LUBRIZOL™5150A, VANLUBE™ SL, NAUGALUBE™ 680, INGANOX™ L-57 and VANLUBE™ 848.VANLUBE™ DND, NAUGALUBE™ 438L, PEARSALL™ OA502 and LUBRIZOL™ 5150Anominally have structures as represented by the above formula wherein D₁and D₂ are C₉ hydrocarbyl groups and E=F=1. VANLUBE™ SL and NAUGALUBE™680 nominally have structures as represented by above formula wherein D₁and D₂ are either one of C₄, C₈ or styryl hydrocarbyl groups and E=F=1;these are mixed diphenyl amines. IRGANOX™ L-57 and VANLUBE™ 848nominally have structures as represented by above formula wherein D₁ andD₂ are either one of t-butyl or t-octyl groups and E=F=1.

Other secondary diarylamines used in this invention soluble in theformulated crankcase oil package include: diphenylamine; variousalkylated diphenylamines; 3-hydroxydiphenylamine;N-phenyl-1,2-phenylenediamine; N-phenyl-1,4-phenylenediamine;monobutyldiphenylamine; dibutyldiphenylamine; monooctyldiphenylamine;monononyldiphenylamine; dinonyldiphenylamine;monotetradecyldiphenylamine; ditetradecyldiphenylamine;phenyl-alpha-naphthylamine; monooctyl phenyl-alpha-naphthylamine;phenyl-beta-naphthylamine; monoheptyldiphenylamine;diheptyldiphenylamine; p-oriented styrenated diphenylamine; mixedbutyloctyldiphenylamine; and mixed octylstryryldiphenylamine, andmixtures thereof. Other examples of commercial diarylamines include, forexample, IRGANOX™ L06, IRGANOX™ L57 (mixed butyloctyl diphenyl amine)and IRGANOX™ L67 from Ciba Specialty Chemicals; NAUGALUBE™ AMS,NAUGALUBE™ 438, NAUGALUBE™ 438R, NAUGALUBE™ 438L, NAUGALUBE™ 500,NAUGALUBE™ 640, NAUGALUBE™ 680, and NAUGARD™ PANA from CromptonCorporation; GOODRITE™ 3123, GOODRITE™ 3190X36, GOODRITE™ 3127,GOODRITE™ 3128, GOODRITE™ 3185X1, GOODRITE™ 3190X29, GOODRITE™ 3190X40,GOODRITE™ 3191 and GOODRITE™ 3192 from Noveon Specialty Chemicals;VANLUBE™ DND, VANLUBE™ NA, VANLUBE™ PNA, VANLUBE™ SL (mixed octylstyryldiphenylamine), VANLUBE™ SLHP, VANLUBE™ SS, VANLUBE™ 81, VANLUBE™ 848,and VANLUBE™ 849, VANLUBE™ 961 (mixed butyloctyl diphenyl amine) from R.T. Vanderbilt Company Inc, LUBRIZOL™ 5150A & C from LUBRIZOL™, andNA-LUBE™ AO-140 (mixed butyloctyl diphenyl amine), NA-LUBE™ AO-150(mixed octylstyryl diphenylamine), from King Industries.

The concentration of the secondary diarylamine in the lubricatingcomposition can vary from about 0.075 to 2.5 wt %, depending upon theapplication. A practical diarylamine use range in the lubricatingcomposition is from about 750 parts per million to 5,000 parts permillion (i.e. 0.075 to 0.5 wt %), preferably from 1,000 to 4,000 partsper million (ppm) and even more preferably from about 1,200 to 3,000 ppm

Preferably, the quantity of tungsten is relation to the quantity of thesecondary amine should be within a certain ratio. The quantity oftungsten should be about 0.020 to 0.6 parts by weight for each part byweight of the amine in the lubricating oil composition. Preferably, thisratio will be from about 0.040 to 0.40 parts of the tungsten per part ofthe amine and particularly about 0.05 to 0.3 parts of the tungsten perpart of the amine. The total quantity of tungsten and amine can beprovided by one or more than one tungsten or amine compound.

An alkylated phenothiazine suitable for this invention is preferably oilsoluble or dispersible and preferably corresponds to the general formulabelow where the substituents R₁₁-R₁₄ could contain heteroatoms,

R₁₁ and R₁₂ are hydrogen or together form a fused six-membered aromaticring; one of R₁₃ and R₁₄ is hydrogen and the other is C₂-C₃₀ alkyl,cyclo-C₅-C₁₂ alkyl, —C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl orα,α-dimethylbenzyl; or both R₁₃ and R₁₄ are C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ hydrogen; or R₁₃ is hydrogen and R₁₄ is C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkylC₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ together form a fused six-membered aromatic ring, R₁₅ is hydrogen,C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or a group —CH₂SR₄, whereR₄ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or an alkylene, aralkylenebridging two phenothiazine moieties.

Typical examples of alkylphenothiazine include but are not limited tomonotetradecylphenothiazine, ditetradecylphenothiazine,monodecylphenothiazine, didecylphenothiazine monononylphenothiazine,dinonylphenothiazine, monoctylphenothiazine and dioctylphenothiazine.

The antioxidant lubrication compositions of the present invention mayoptionally contain additional friction modifiers, antioxidants and/orcopper corrosion inhibitors. Embodiments of friction modifiers which mayoptionally be added can be found for example in U.S. Pat. Nos. 4,792,410and 5,110,488, which are incorporated herein by reference in theirentirety and include fatty phosphites, fatty acid amides, fattyepoxides, borated fatty epoxides, fatty amines, glycerol esters, boratedglycerol esters, alkoxylated fatty amines, borated alkoxylated fattyamines, metal salts of fatty acids, sulfurized olefins, fattyimidazolines and mixtures thereof.

Embodiments of antioxidants which may optionally be added includehindered phenolic antioxidants, secondary aromatic amine antioxidants,sulfurized phenolic antioxidants, oil-soluble copper compounds,phosphorus-containing antioxidants, organic sulfides, disulfides andpolysulfides.

Embodiments of copper corrosion inhibitors which may optionally be addedinclude thiazoles, triazoles and thiadiazoles. Example embodiments ofsuch compounds include benzotriazole, tolyltriazole, octyltriazole,decyltriazole, dodecyltriazole, 2-mercapto benzothiazole,2,5-dimercapto-1,3,4-thiadiazole,2-mercapto-5-hydrocarbylthio-1,3,4-thiadiazoles,2-mercapto-5-hydrocarbyldithio-1,3,4-thiadiazoles,2,5-bis(hydrocarbylthio)-1,3,4-thiadiazoles, and2,5-bis(hydrocarbyldithio)-1,3,4-thiadiazoles.

The organotungsten compound, alkylated diphenylamine and sulfurcontaining compound can either be added individually to a base oil toform the lubricating composition of the invention or they can bepremixed to form a composition which can then be added to the base oil.The resulting lubricating composition preferably comprises a majoramount (i.e. at least 90% by weight) of base oil and a minor amount(i.e. less than 10% by weight) of the additive composition.

In another aspect the invention provides for a lubricating oilcomposition which comprises lubricating oil and a lubricating oiladditive comprising the combination of an oil-soluble tungsten compoundand at least one oil-soluble aromatic amine. The concentration of thelubricating oil additive is typically in the range of 0.01 to about 15%by weight based on the total weight of the composition and is preferablyfrom about 0.1 to about 7% by weight.

Suitable lubricating oils for use in preparing the lubricatingcomposition include those oils which are conventionally employed ascrankcase lubricating oils for internal combustion engines and thosewhich may be employed as power transmitting fluids such as automatictransmission fluids, hydraulic fluids, or gear lubricants.

The lubricating oil may be a synthetic oil such as for examplealkylesters of dicarboxylic acids, polyglycols and alcohols,polyalphaolefins, alkylbenzenes, alkyl naphthalenes, organic esters ofphosphoric acids, or polysilicone oils. The lubricating oil may be anatural oil including mineral oils which may vary widely as to theircrude source e.g. whether paraffinic, naphthenic or mixedparaffinic-naphthenic; as well as to their formation, e.g. distillationrange, straight run or cracked, hydrorefined, or solvent extracted.

The invention further provides a lubricating oil concentrate. In thepreparation of lubricating oil compositions it is a convenient practiceto introduce additives in the form of a concentrate; which introductionmay be made by methods known in the art. The lubricating oil concentratemay contain between 2.5 to 90 weight percent more preferably 5 to 75weight percent of the additive composition in a suitable solvent.Suitable solvents may include hydrocarbon oils (e.g. mineral lubricatingoil or synthetic oil).

The ratio of tungsten compound to the oil-soluble aromatic amine may beselected so as to provide an antioxidant effect of sufficient magnitudeto meet the end use requirements of the lubricating oil—for example, toachieve adequate performance in the Sequence III E engine test forcrankcase lubricating oils (according to the procedure of ASTM STP315).Preferably the tungsten compound and the oil-soluble aromatic amine areemployed in a ratio of from 1:10 to 10:1 (by wt), more preferably from3:1 to 1:3 (by wt).

The lubricating oil additive may be used as the sole additive for thecomposition or concentrate or may be used in combination with severaldifferent types of additives which may be required to fulfill otherrequirements of the composition or concentrate during use. Thecomposition may be used as a crankcase lubricating oil, a cylinderlubricant for applications such as marine diesel, industrial oil,functional fluid such as power transmission fluid, tractor oil, gear oilor hydraulic fluid. Accordingly the compositions or concentrates of theinvention may in addition to the lubricating oil additive contain one ormore of the following:

(a) a dispersant, preferably an ashless dispersant;

(b) a metal containing detergent, preferably having a high total basenumber;

(c) an antiwear and/or extreme pressure additive;

(d) a viscosity index improver, which may also have dispersantproperties;

(e) a pour point depressant;

(f) a corrosion inhibitor and/or metal deactivator; and

(g) a friction modifier or fuel economy agent,

as well as other additives such as demulsifiers, seal swell agents, oreven supplementary antioxidants.

Where such compositions are for use as crankcase lubricants theypreferably contain at least an ashless dispersant and/or a viscosityindex improver dispersant, a detergent, and an antiwear additive inamounts effective to provide their respective functions.

Dispersants

The preferred ashless dispersant in the compositions and concentrates ofthis invention is a long chain hydrocarbyl substituted mono- ordi-carboxylic acid material, (i.e. acid, anhydride, or ester) andincludes a long chain hydrocarbon, generally a polyolefin, substitutedwith an alpha or beta unsaturated C4 to C10 carboxylic acid material,such as itaconic acid, maleic acid, maleic anhydride, chloromaleic acid,dimethyl fumarate, chloromaleic anhydride, acrylic acid, methacrylicacid, crotonic acid, or cinnamic acid. Preferably, the dispersantcontains at least about 1 mole (e.g. 1.05 to 1.2 moles, or higher) ofthe acid material per mole of polyolefin. The proportion of thedispersant is preferably from 1 to 10, and even more preferably 3 to 7weight percent of the lubricating oil.

Preferred olefin polymers for the reaction with carboxylic acids arepolymers derived from a C2 to C5 monoolefin. Such olefins includeethylene, propylene, butylene, isobutylene, pentene, oct-1-ene orstyrene. The polymers may be homopolymers such as polyisobutylene orcopolymers of two or more of such olefins. These include copolymers ofethylene and propylene; butylene and isobutylene; propylene andisobutylene; etc. Other copolymers include those in which a minor molaramount of the copolymer monomers (e.g. 1 to 10 mole percent), is a C4 toC18 diolefin, (e.g., a copolymer of isobutylene and butadiene; or acopolymer of ethylene, propylene and 1,4-hexadiene; etc).

In some cases, the olefin polymer may be completely saturated, forexample an ethylene-propylene copolymer made by a Ziegler-Nattasynthesis using hydrogen as a moderator to control molecular weight.

The olefin polymers usually have number average molecular weights aboveabout 700, including number average molecular weights within the rangeof from 1,500 to 5,000 with approximately one double bond per polymerchain. An especially suitable starting material for a dispersantadditive is polyisobutylene. The number average molecular weight forsuch polymers can be determined by several known techniques. Aconvenient method for such determination is by gel permeationchromatography (GPC) which additionally provides molecular weightdistribution information. (see W. W. Yau, J. J. Kirkland and D. D. Bly,“Modern Size Exclusion Liquid Chromatography,” John Wiley and Sons, NewYork, 1979).

Processes for the reaction of the olefin polymer with the unsaturatedcarboxylic acid, anhydride, or ester are known in the art. For example,the olefin polymer and the carboxylic acid material may be simply heatedtogether as disclosed in U.S. Pat. Nos. 3,361,673 and 3,401,118 (herebyincorporated by reference in their entirety) to cause a thermal “ene”reaction to take place. Alternatively, the olefin polymer can be firsthalogenated, for example chlorinated or brominated, to about 1 to 8,preferably 3 to 7, weight percent chlorine or bromine, based on theweight of polymer, by passing chlorine or bromine through the polyolefinat a temperature of 100° C. to 250° C., e.g. 120° C. to 160° C., forabout 0.5 to 10 hours, more preferably 1 to 7 hours. The halogenatedpolymer may then be reacted with sufficient unsaturated acid oranhydride at 100° to 250° C., usually 180° C. to 220° C., for 0.5 to 10hours, more preferably 3 to 8 hours. Processes of this general type aretaught in U.S. Pat. Nos. 3,087,436; 3,172,892; 3,272,746, herebyincorporated by reference in their entirety.

Alternatively, the olefin polymer and the unsaturated acid or anhydrideare mixed and heated while chlorine is added to the hot material.Processes of this type are disclosed in U.S. Pat. Nos. 3,215,707;3,231,587; 3,912,764; 4,110,349; 4,234,435; and GB-A-1 440 219, all ofwhich are incorporated by reference in their entirety.

When a halogen is used, from 65 to 95 weight percent of the polyolefinnormally reacts with the carboxylic acid or anhydride. Thermalreactions, carried out without the use of halogen or a catalyst, causeonly from 50 to 75 weight percent of the polyisobutylene to react.Chlorination increases reactivity.

The carboxylic acid or anhydride can then be further reacted withamines, alcohols, including polyols, amino-alcohols, etc., to form otheruseful dispersant additives. Thus if the acid or anhydride is to befurther reacted, (e.g. neutralized) then generally a major proportion ofat least 50 percent of the acid units up to all the acid units will bereacted.

The ashless dispersants useful in this invention are polyisobutenylsuccinimides formed from polyisobutenyl succinic anhydride and analkylene polyamine such as triethylene tetramine or tetraethylenepentamine, wherein the polyisobutenyl substituent is derived frompolyisobutene having a number average molecular weight preferably in therange of 700 to 1200 more preferably from 900 to 1100. It has been foundthat selecting certain dispersants within the broad range of alkenylsuccinimides produces fluids with improved frictional characteristics.The most preferred dispersants of this invention are those wherein thepolyisobutene substituent group has a molecular weight of approximately950 atomic mass units, the basic nitrogen containing moiety is polyamine(PAM) and the dispersant has been post treated with a boronating agent.

The ashless dispersants of the invention can be used in any effectiveamount. However, they are typically used from about 0.1 to 10.0 masspercent in the finished lubricant, preferably from about 0.5 to 7.0percent, and most preferably from about 2.0 to about 5.0 percent.

Useful amine compounds for reaction with the hydrocarbyl substitutedcarboxylic acid or anhydride include mono- and polyamines withpreferably 2 to 60, and more preferably 3 to 20, total carbon atoms andfrom 1 to 12, and more preferably 2 to 8 nitrogen atoms in a molecule.These amines may be hydrocarbyl amines or may be hydrocarbyl aminesincluding other groups, e.g. hydroxy groups, alkoxy groups, amidegroups, nitriles, or imidazoline groups. Hydroxy amines with 1 to 6hydroxy groups, preferably 1 to 3 hydroxy groups, are particularlyuseful. Preferred amines are aliphatic saturated amines, including thoseof the general formulae:

wherein R²⁸, R²⁹ and R³⁰ are each independently hydrogen; C₁ to C₂₅straight or branched chain alkyl radicals; C₁ to C₁₂ alkoxy-(C₆alkylene) radicals; or C₂ to C₁₂ alkylamino-C₂ to C₆ alkylene) radicals;each s₁ can be the same or a different number of from 2 to 6, preferably2 to 4; and w is a number from 0 to 10, preferably 2 to 7. Preferably atleast one of R²⁸, R²⁹ and R³⁰ is hydrogen.

Suitable amines include 1,2-diaminoethane; 1,3-diaminopropane;1,4-diaminobutane; 1,6-diaminohexane; polyethylene amines such asdiethylene triamine; triethylene tetramine; tetraethylene pentamine;polypropylene amines such as 1,2-propylene diamine;di-(1,2-propylene)triamine; di(1,3-propylene)-triamine;N,N-dimethyl-1,3-diaminopropane; N,N-di-(2-aminoethyl)ethylene diamine;N,N-di(2-hydroxyethyl)-1,3-propylene diamine; 3-dodecyloxypropylamine;N-dodecyl-1,3-propane diamine; tris hydroxymethylaminomethane (THAM);diisopropanol amine; diethanol amine; triethanol amine; aminomorpholines such as N-(3-amino-propyl)morpholine; etc.

Other useful amine compounds include alicyclic diamines such as1,4-di-(aminomethyl)cyclohexane, and heterocyclic nitrogen compoundssuch as imidazolines, and N-aminoalkyl piperazines of the generalformula:

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3. Examples of such amines include 2-pentadecyl imidazolineand N-(2-aminoethyl)piperazine.

Hydroxyamines which can be reacted with the long chain hydrocarbonsubstituted dicarboxylic acid material mentioned above to formdispersants include 2-amino-1-butanol, 2-amine-2-methyl-1-propanol,p-(beta-hydroxyethyl)-aniline, 2-amino-1-propanol, 3-amino-1-propanol,2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol,N-(beta-hydroxy propyl)N′-(beta-aminoethyl)-piperazine, ethanolamine andbeta-(beta-hydroxyethoxy)-ethylamine. Mixtures of these or similaramines can also be employed. Commercial mixtures of amine compounds mayadvantageously be used. For example, one process for preparing alkyleneamines involves the reaction of an alkylene dihalide (such as ethylenedichloride or propylene dichloride) with ammonia, which results in acomplex mixture of alkylene amines wherein pairs of nitrogens are joinedby alkylene groups, forming such compounds as diethylene triamine,triethylene tetramine, tetraethylene pentamine and correspondingpiperazines. Useful poly(ethyleneamine) compounds averaging about 5 to 7nitrogen atoms per molecule are available commercially under trade namessuch as “Polyamine H”, “Polyamine 400”, “Dow Polyamine E-100”, etc.

Useful amines also include polyoxyalkylene polyamines such as those ofthe formulae:

(i) NH₂-alkylene(O-alkylene)m NH₂ where m has a value of from 3 to 70,preferably 10 to 35; and

(ii) R-(alkylene(O-alkylene)n NH2)3-6 where each n has a value of about1 to 40, with the proviso that the sum of all the n's is from 3 to 70and preferably from 6 to 35, and R is a saturated hydrocarbon radical ofup to ten carbon atoms, wherein the number of substituents on the Rgroup is from 3 to 6. The alkylene groups in either formula (i) or (ii)may be straight or branched chains containing about 2 to 7, andpreferably about 2 to 4, carbon atoms.

The polyoxyalkylene polyamines above, preferably polyoxyalkylenediamines and polyoxyalkylene triamines, may have average molecularweights ranging from 200 to 4,000 and preferably from 400 to 2,000. Thepreferred polyoxyalkylene polyamines include the polyoxyethylene andpolyoxypropylene diamines and the polyoxypropylene triamines havingaverage molecular weights ranging from 200 to 2,000. The polyoxyalkylenepolyamines are commercially available and may be obtained, for example,from the Jefferson Chemical Company, Inc. under the trade name“Jeffamines D-230, D400, D-1000, D-2000, T-403,” etc.

The amine is readily reacted with the carboxylic acid material, e.g.alkenyl succinic anhydride, by heating an oil solution containing 5 to95 weight percent of carboxylic acid material to from 100 to 250° C.,preferably 125 to 175° C., generally for 1 to 10 hours, more preferablyfrom 2 to 6 hours, until the desired amount of water has been removed.The heating is preferably carried out to favor formation of imides, ormixtures of imides and amides, rather than amides and salts. Reactionratios can vary considerably, depending upon the reactants, amounts ofexcess amine, type of bonds formed, etc. Generally from 0.3 to 2 molesof amine, more preferably from 0.3 to 1.0 moles of amine, and even morepreferably 0.4 to 0.8 mole of amine (e.g. bis-primary amine) is used permole of the carboxylic acid moiety content (e.g. grafted maleicanhydride content). For example, one mole of olefin reacted withsufficient maleic anhydride to add 1.10 mole of maleic anhydride groupsor mole of olefin when converted to a mixture of amides and imides,about 0.55 moles of amine with two primary groups would preferably beused, i.e. 0.50 mole of amine per mole of dicarboxylic acid moiety.

The nitrogen-containing dispersant can be further treated by boration asgenerally taught in U.S. Pat. Nos. 3,087,936 and 3,254,025, herebyincorporated by reference in their entirety.

Tris(hydroxymethyl)amino methane (THAM) can be reacted with theaforesaid acid material to form amides, imides or ester type additivesas taught by GB-A-984 409, or to form oxazoline compounds and boratedoxazoline compounds as described, for example, in U.S. Pat. Nos.4,102,798, 4,116,876 and 4,113,639, hereby incorporated by reference intheir entirety.

The ashless dispersants may also be esters derived from the long chainhydrocarbyl substituted carboxylic acid material and from hydroxycompounds such as monohydric and polyhydric alcohols or aromaticcompounds such as phenols and naphthols, etc. The polyhydric alcoholsare the most preferred hydroxy compound and preferably contain from 2 to10 hydroxy radicals, for example, ethylene glycol, diethylene glycol,triethylene glycol, tetraethylene glycol, dipropylene glycol, and otheralkylene glycols in which the alkylene radical contains from 2 to 8carbon atoms. Other useful polyhydric alcohols include glycerol,mono-oleate of glycerol, monostearate of glycerol, monomethyl ether ofglycerol, pentaerythritol, dipentaerythritol, etc.

The ester dispersant may also be derived from unsaturated alcohols suchas allyl alcohol, cinnamyl alcohol, propargyl alcohol,1-cyclohexane-3-ol, and oleyl alcohol. Still other classes of alcoholscapable of yielding the esters comprise the ether-alcohols andamino-alcohols including, for example the oxy-alkylene-, oxy-arylene-,amino-alkylene-, and amino-arylene-substituted alcohols having one ormore oxy-alkylene, amino-alkylene or amino-arylene or amino-aryleneoxy-arylene radicals. They are exemplified by Cellosolve, carbitol,N,N,N′,N′-tetrahydroxy-tri-methylene di-amine, and ether-alcohols havingup to about 150 oxyalkylene radicals in which each alkylene radicalcontains from 1 to 8 carbon atoms.

The ester dispersant may be a di-ester of succinic acid or an acidicester (i.e. a partially esterified succinic acid), or a partiallyesterified polyhydric alcohol or phenol, (i.e. an ester having freealcoholic or phenolic hydroxyl radicals). Mixtures of the aboveillustrated esters are likewise contemplated.

The ester dispersant may be prepared by one of several known methods asillustrated for example in U.S. Pat. No. 3,381,022, hereby incorporatedby reference in their entirety.

Mannich base type dispersants such as those described in U.S. Pat. Nos.3,649,229 and 3,798,165 (hereby incorporated by reference in theirentirety) may also be used in these compositions. Such Mannich basedispersants can be formed by reacting a high molecular weight,hydrocarbyl-substituted mono- or polyhydroxylbenzene (e.g. having anumber average molecular weight of 1,000 or greater) with amines (e.g.polyalkyl polyamines, polyalkenyl polyamines, aromatic amines,carboxylic acid-substituted polyamines and the succinimide formed fromany one of these with an olefinic succinic acid or anhydride) andcarbonyl compounds (e.g. formaldehyde or para formaldehyde).

A particularly suitable dispersant is one derived from polyisobutylenesubstituted with succinic anhydride groups and reacted with polyethyleneamines, e.g. tetraethylene pentamine, pentaethylene hexamine,polyoxyethylene and polyoxypropylene amines, e.g. polyoxypropylenediamine, trismethylolaminomethane and pentaerythritol, and combinationsthereof

Detergents

Metal-containing rust inhibitors and/or detergents are frequently usedwith ashless dispersants. Such detergents and rust inhibitors includeoil-soluble mono- and dicarboxylic acids, the metal salts of sulfonicacids, alkyl phenols, sulfurized alkyl phenols, alkyl salicylates andnaphthenates in neutral or basic form. Highly basic (or “over-based”)metal salts, which are frequently used as detergents, appearparticularly prone to promote oxidation of hydrocarbon oils containingthem. Usually these metal-containing rust inhibitors and detergents areused in lubricating oil in amounts of from 0.01 to 10 weight percent,more preferably from 0.1 to 5 weight percent, based on the weight of thetotal lubricating composition.

Highly basic alkali metal and alkaline earth metal sulfonates arefrequently used as detergents. They are usually produced by heating amixture comprising an oil-soluble sulfonate or alkaryl sulfonic acid,with an excess of alkali metal or alkaline earth metal compound abovethat required for complete neutralization of any sulfonic acid presentand thereafter forming a dispersed carbonate complex by reacting theexcess metal with carbon dioxide to provide the desired overbasing. Thesulfonic acids are typically obtained by the sulfonation of alkylsubstituted aromatic hydrocarbons such as those obtained from thefractionation of petroleum by distillation and/or extraction or by thealkylation of aromatic hydrocarbons as for example those obtained byalkylating benzene, toluene, xylene, naphthalene, diphenyl and thehalogen derivatives such as chlorobenzene, chlorotoluene andchloronaphthalene. The alkylation may be carried out in the presence ofa catalyst with alkylating agents having from about 3 to more than 30carbon atoms. For example, haloparaffins, olefins obtained bydehydrogenation of paraffins, polyolefin polymers produced fromethylene, propylene, etc. are all suitable. The alkaryl sulfonatesusually contain from 9 to 70 or more carbon atoms, preferably from 16 to50 carbon atoms per alkyl substituted aromatic moiety.

The alkali metal or alkaline earth metal compounds which may be used inneutralizing these alkaryl sulfonic acids to provide the sulfonatesinclude the oxides and hydroxides, alkoxides, carbonates, carboxylates,sulfides, hydrosulfides, nitrates, borates and ethers of sodium,magnesium, calcium, strontium and barium. Non-limiting examples includecalcium oxide, calcium hydroxide, magnesium oxide, magnesium acetate,and magnesium borate. As noted, the alkaline earth metal compound isused in excess of that required to complete neutralization of thealkaryl sulfonic acids. Generally, the amount ranges from 100 to 220percent, although it is preferred to use at least 125 percent of thestoichiometric amount of metal required for complete neutralization.

Various other preparations of basic alkali metal and alkaline earthmetal alkaryl sulfonates are known, such as those described in U.S. Pat.Nos. 3,150,088 and 3,150,089 (hereby incorporated by reference in theirentirety) wherein overbasing is accomplished by hydrolysis of analkoxide-carbonate complex with the alkaryl sulfonate in a hydrocarbonsolvent-diluent oil.

Preferred alkaline earth sulfonate additives are magnesium alkylaromatic sulfonate additives having a high total base number (TBN) asmeasured by ASTM 02896 of at least 250, more preferably ranging from 300to 400, and calcium alkyl aromatic sulfonates having a TBN of at least250, preferably from 300-400.

Neutral metal sulfonates are frequently used as rust inhibitors.Polyvalent metal alkyl salicylate and naphthenate materials are knownadditives for lubricating oil compositions to improve their hightemperature performance and to counteract deposition of carbonaceousmatter on pistons (e.g. U.S. Pat. No. 2,744,069, hereby incorporated byreference in their entirety). An increase in reserve basicity of thepolyvalent metal alkyl salicylates and naphthenates can be realized byutilizing alkaline earth metal, e.g. calcium, salts of mixtures ofC₈-C₂₆ alkyl salicylates and phenates (e.g. U.S. Pat. No. 2,744,069,hereby incorporated by reference in their entirety) or polyvalent metalsalts of alkyl salicylic acids, said acids obtained from the alkylationof phenols followed by phenation, carboxylation and hydrolysis (e.g.U.S. Pat. No. 3,704,315, hereby incorporated by reference in theirentirety) which could then be converted into highly basic salts bytechniques generally known and used for such conversion. The reservebasicity of these metal-containing rust inhibitors is useful at TBNlevels of between 60 and 150. Non-limiting examples of useful polyvalentmetal salicylate and naphthenate materials are the methylene and sulfurbridged materials which are readily derived from alkyl substitutedsalicylic or naphthenic acids or mixtures of either or both with alkylsubstituted phenols. Basic sulfurized salicylates and a method for theirpreparation are disclosed in U.S. Pat. No. 3,595,791, herebyincorporated by reference in their entirety. Such materials includealkaline earth metal, particularly magnesium, calcium, strontium andbarium, salts of aromatic acids having the general formula:HOOC—ArR³¹OH-Q_(k)(ArR³¹OH)rwhere Ar is an aryl radical of 1 to 6 rings, R31 is an alkyl grouphaving from 8 to 50 carbon atoms, preferably 12 to 30 carbon atoms(optimally about 12), Q is a sulfur (—S—) or methylene (—CH₂—) bridge, kis a number from 0 to 4 and r is a number from 0 to 4.

Preparation of the overbased methylene bridged salicylate-phenate saltis readily carried out by conventional techniques such as by alkylationof a phenol followed by phenation, carboxylation, hydrolysis, methylenebridging a coupling agent such as an alkylene dihalide followed by saltformation concurrent with carbonation. An overbased calcium salt of amethylene bridged phenol-salicylic acid with a TBN of 60 to 150 is alsouseful.

Another type of basic metal detergent, the sulfurized metal phenates,can be considered a metal salt whether neutral or basic, of a compoundtypified by the general formula:

where j=1 or 2, q=0, 1 or 2 or a polymeric form of such a compound,where Rp is an alkyl radical, j and q are each integers from 1 to 4, andthe average number of carbon atoms in all of the R groups is at leastabout 9 in order to ensure adequate solubility in oil. The individual Rpgroups may each contain from 5 to 40, preferably 8 to 20, carbon atoms.The metal salt is prepared by reacting an alkyl phenol sulfide with asufficient quantity of metal containing material to impart the desiredalkalinity to the sulfurized metal phenate.

Regardless of the manner in which they are prepared, the sulfurizedalkyl phenols which are useful generally contain from 2 to 14 percent byweight, preferably 4 to 12 weight percent sulfur based on the weight ofsulfurized alkyl phenol. The sulfurized alkyl phenol may be converted byreaction with a metal-containing material including oxides, hydroxidesand complexes in an amount sufficient to neutralize said phenol and, ifdesired, to overbase the product to a desired alkalinity by procedureswell known in the art. Preferred is a process of neutralizationutilizing a solution of metal in glycol ether.

The neutral or normal sulfurized metal phenates are those in which theratio of metal to phenol nucleus is about 1:2. The “overbased” or“basic” sulfurized metal phenates are sulfurized metal phenates whereinthe ratio of metal to phenol is greater than the stoichiometric ratio,e.g. basic sulfurized metal dodecyl phenate has a metal content up to(or greater) than 100 percent in excess of the metal present in thecorresponding normal sulfurized metal phenate. The excess metal isproduced in oil-soluble or dispersible form (as by reaction with CO₂).

The detergents which may be included in the compositions of the presentinvention may optionally be borated in a known manner. Such borationprovides the detergent with a measure of anti-wear activity.

It is preferred to use a combination of metal-containing detergentscomprising calcium and magnesium salts or calcium, magnesium and sodiumsalts, as described above.

Antiwear Additives (Including Extreme Pressure Agents)

A wide variety of anti-wear additives may be included in thecompositions or concentrates of the invention. For example, organicsulfides and polysulfides including especially dialkyl sulfides andpolysulfides (e.g. dibutyl polysulfides, and dibenzyl sulfides andpolysulfides) which may be substituted (e.g. with halogen, may beincorporated in the compositions or concentrates). Sulfurized esters,(e.g. sulfurized methyl or isopropyl oleate) and other sulfurizedcompounds, (e.g. sulfurized olefins such as sulfurized diisobutylene,sulfurized tripropylene or sulfurized dipentene) may also be added tothe compositions. More complex sulfurized compounds such as sulfurizedalkyl phenols and sulfurized terpenes and Diels-Alder adducts andsulfurized polymers, e.g. butadiene/butyl acrylate copolymers, may alsobe used, as may sulfurized tall oil fatty acid esters. Esters ofbeta-thiodipropionic acid, e.g. butyl, nonyl, tridecyl or eicosyl estersmay also be used.

Anti-wear additives in the form of phosphorus esters, (e.g. di- andtri-alkyl, cycloalkyl or aryl phosphites) may also be used. Examples ofsuch phosphites include dibutyl phosphite, dihexyl phosphite,dicyclohexyl phosphite, alkyl phenyl phosphites such as dimethylphenylphosphite and mixed higher alkyl, (e.g. oleyl, alkyl phenyl phosphate,an example of which includes 4-pentyl phenyl phosphite). Phosphitesbased on polymers such as low molecular weight, polyethylenes andpolypropylenes may also be used.

Preferred anti-wear additives for addition to the compositions andconcentrates of the present invention are the dihydrocarbyldithiophosphate metal salts. They also provide some antioxidantactivity. The zinc salts are most commonly used in lubricating oils inamounts of 0.1 to 10, preferably 0.2 to 2, weight percent, based uponthe total weight of the lubricating oil composition. Salts of othermetals, e.g. barium and cadmium, can also be used. They may be preparedin accordance by first forming a dithiophosphoric acid, usually byreaction of an alcohol or a phenol with P2 S5 and then neutralizing thedithiophosphoric acid with a suitable zinc compound.

Alcohols may be used including mixtures of primary and secondaryalcohols, with secondary alcohol generally for imparting improvedantiwear properties, and primary alcohols forgiving improved thermalstability properties. Mixtures of the two are particularly useful. Ingeneral, any basic or neutral zinc compound could be used but theoxides, hydroxides and carbonates are most generally employed.Commercial additives frequently contain an excess of zinc due to use ofan excess of the basic zinc compound in the neutralization reaction.

The zinc dihydrocarbyl dithiophosphates useful in the present inventionare oil-soluble salts of dihydrocarbyl esters of dithiphosphoric acidsand may be represented by the following formula

wherein A¹² and A¹³ may be the same or different hydrocarbyl radicalscontaining from 1 to 18, preferably 2 to 12, carbon atoms and includingradicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl andcycloaliphatic radicals. Particularly preferred as A¹² and A¹³ groupsare alkyl groups of 2 to 8 carbon atoms. Thus, the radicals may, forexample be ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, amyl,s-hexyl, i-hexyl, i-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl,nonyl-phenyl, dodecyl-cyclohexyl, methylcyclopentyl, propenyl, butenyl,etc. In order to obtain oil solubility, the total number of carbon atomsin the dithiophosphoric acid (i.e. A¹² and A¹³) generally should beabout 5 or greater and preferably 8 or greater.

Borated derivatives of the aforesaid antiwear agents may also beincluded in the compositions or concentrates of the invention.

Thiadiazole

The 1,3,4-thiadiazoles of formula I may be prepared by the methoddisclosed in U.S. Pat. Nos. 4,761,482 and 4,880,437, incorporated hereinby reference in their entirety:

wherein T¹ and T² are independently selected from the group consistingof hydrogen, alkyl, hydroxyalkyl, alkylthio, phenylalkyl, alkylatedphenylalkyl, terpene residue and maleic acid residue of the formula

wherein R³² and R³³ are independently selected from the group consistingof hydrogen, branched or straight chain alkyl groups and cyclicaliphatic groups, wherein at least one of R³² and R³³ is not hydrogen.

An embodiment for the present invention includes alkyls which have from1 to 50 carbon atoms which may be branched or straight chain and may besubstituted with a hydroxyl group and an aryl group. Another embodimentfor the present invention are T¹ and T² which are alkyl and alkylthiogroups which contain 1 to 22 carbon atoms and may be branched orstraight chain. Additional embodiments for the present invention includecompounds wherein T¹ and T² together contain a total of at least 22carbon atoms in their alkyl and/or alkylthio groups.

Embodiments of terpene residues for the present invention includeterpenes which are derived from pinene and limonene.

An embodiment of maleic acid residues for the present invention includemaleic acid residues where R³² and R³³ independently represents an alkylgroup with 1 to 22 carbon atoms or C₅-C₇ cycloalkyl group. A furtherembodiment includes the total number of carbon atoms for R³² and R³³combined being from 8 to 44 carbon atoms.

Commercially available thiadiazoles derivatives are VANLUBE® 871(butanedioicacid((4,5-dihydro-5-thioxo-1,3,4-thiadiazol-2-yl)thio-bis(2-ethylhexyl)ester)CUVAN® 826 (2,5-dimercapto-1,3,4-thiadiazole) and CUVAN® 484(alkylthiadiazole) manufactured by R. T. Vanderbilt Company, Hitec™4313, 4312, RC 8210, and RC 8213.

Dithiocarbamates

(i) Bisdithiocarbamates

The bisdithiocarbamates of formula are known compounds described in U.S.Pat. No. 4,648,985, incorporated herein by reference in its entirety.

The compounds are characterized by R³⁴, R³⁵, R³⁶ and R³⁷ which are thesame or different and are hydrocarbyl groups having 1 to 13 carbonatoms.

Embodiments for the present invention include bisdithiocarbamateswherein R³⁴, R³⁵, R³⁶ and R³⁷ are the same or different and are branchedor straight chain alkyl groups having 1 to 8 carbon atoms.

R³⁸ is an aliphatic group such as straight and branched alkylene groupscontaining 1 to 8 carbons. An embodiment for R³⁸ ismethylenebis(dibutyldithiocarbamate) available commercially from R. T.Vanderbilt Company, Inc. under the tradename VANLUBE® 7723, and fromKing Industries under the tradename NA-LUBE® ADTC.(ii) Ashless Dithiocarbamate Esters

The compounds of the above formula are characterized by groups R³⁹, R⁴⁰,R⁴¹ and R⁴² which are the same or different and are hydrocarbyl groupshaving 1 to 13 carbon atoms. VANLUBE® 732 and VANLUBE.® 981 arecommercially available from R. T. Vanderbilt Company, Inc.(iii) Metal Dithiocarbamates

The dithiocarbamates of the above formula are known compounds. One ofthe processes of preparation is disclosed in U.S. Pat. No. 2,492,314,which is hereby incorporated by reference in its entirety. Rd and Rerepresent branched or straight chain alkyl groups having 1 to 8 carbonatoms, M is a metal cation and n is an integer based upon the valency ofthe metal cation (e.g. n=1 for sodium (Na⁺); n=2 for zinc (Zn⁺⁺); etc.).Molybdenum dithiocarbamate processes are described in U.S. Pat. Nos.3,356,702; 4,098,705; and 5,627,146, each of which is herebyincorporated by reference. Substitution is described as branched orstraight chain ranging from 8 to 13 carbon atoms in each alkyl group.

Embodiments for the present invention include metal dithiocarbamateswhich are antimony, zinc and tungsten dithiocarbamates.

Additionally the lubricant composition may also include phosphorousdithiophosphate compounds. Embodiments of dithiophosphates for thepresent invention include:(i) Metal Phosphorodithioates

The metal phosphorodithioates are known, commercially availablematerials. One of the processes of preparation is taught by U.S. Pat.No. 4,215,067, which is hereby incorporated by reference in itsentirety. (M and n are as defined above for the metal dithiocarbamates)R^(f) and R^(g) represent branched and straight chain alkyl groupshaving 1-22 groups and may be derived from fatty acids. In oneembodiment the metal phosphorodithioates are zinc phosphorodithioates.The metal ion in formula V may be selected from the following groups ofthe Periodic Table: IIA, IIIA, VA, VIA, IB, IIB, VIB and VIII. Aminesalts of the compounds are also useful synergists of the invention.Embodiments of such amine salts include those prepared from alkyl aminesand mixed alkyl amines. An additional embodiment includes amine saltsbased on fatty acid amines.(ii) Phosphorodithioate esters

The phosphorodithioate esters are known compounds. One of the processesof manufacture is disclosed in U.S. Pat. No. 3,567,638, which is herebyincorporated by reference in its entirety. R^(j), R^(k), R^(l) and R^(m)may be the same or different and may be branched and straight chainalkyl groups. Embodiments for the present invention include branched orstraight chain alkyl groups containing 1 to 8 carbon atoms.

Embodiments for the ranges of phosphorodithioate (also known asdithiophosphate) compound, or mixture of dithiophosphate compounds, are0.05-2.00%; 0.5-1.50%; and 0.5-0.8% (each percentage being percent byweight based upon the total weight of the composition).

Additional Antioxidants

Additional antioxidants which are especially useful in lubricating oilcompositions or concentrates are based on oil-soluble copper compounds,e.g. in the form of a synthetic or natural carboxylic acid salt. By“oil-soluble” is meant that the compound is oil-soluble or solubilizedunder normal blending conditions in the oil or concentrate. Examples ofoil-soluble copper compounds include salts of C₁₀ to C₁₈ fatty acidssuch as stearic or palmitic acid; but unsaturated acids (such as oleicacid), branched carboxylic acids (such as naphthenic acids) of molecularweight from 200 to 500, dicarboxylic acids such as polyisobutenylsuccinic acids, and synthetic carboxylic acids can all be used becauseof the acceptable handling and solubility properties of the resultingcopper carboxylates.

Suitable oil-soluble copper dithiocarbamates have the general formula

where p is 1 or 2 and R44 and R45 may be the same or differenthydrocarbyl radicals containing from 1 to 18 carbon atoms each andincluding radicals such as alkyl, alkenyl, aryl, aralkyl, alkaryl andcycloaliphatic radicals. Particularly preferred as R⁴⁴ and R⁴⁵ groupsare alkyl groups of 2 to 8 carbon atoms. Thus, the radicals may be, forexample, ethyl, n-propyl, n-butyl, i-butyl, sec-butyl, amyl, sec-hexyl,i-hexyl, i-octyl, decyl, dodecyl, octadecyl, 2-ethylhexyl, nonyl-phenyl,dodecyl-phenyl, cyclohexyl, methylcyclopentyl, propenyl, butenyl, etc.In order to obtain oil solubility, the total number of carbon atoms(i.e. R⁴⁴ and R⁴⁵) generally should be about 5 or greater.

Copper salts of dithiophosphonic acids (the acid as describedhereinbefore in relation to antiwear additives specifically as zincsalts), copper sulfonates, phenates, copper polyisobutylene succinicanhydride (“Copper PIBSA”) carboxylates such as oleates, stearates andmixtures thereof, and acetyl acetonates can also be used.

These antioxidants can be used in amounts such that, in the finallubricating composition, a copper concentration of from 5 to 500 ppm ispresent.

Other known oil-soluble or oil-ispersible, and preferably liquid,antioxidants may also be used in the compositions of the invention.Examples of such antioxidants include hindered phenols, which maycontain sulphur, e.g. 4,4′-methylene bis(2,6-di(t-butyl)phenol),4,4′-thio bis(2,6-di(t-butyl)phenol) and p-alkylated hindered phenols;unhindered phenols which again may contain sulphur such as 2,2′-thiobis-(4-nonyl phenol) and 2,2′-methylene bis(4-nonylphenol);phenothiazine derivatives, e.g. those containing higher alkylsubstituents such as dioctyl and dinonyl phenothiazines; substitutedalpha and betanaphthyl amines such as phenyl beta-naphthylamine and itsalkylated derivatives; other amino aryl compounds such as for example4,4′-bis(secbutylamino)diphenylmethane; dithiocarbamates such as zinc,nickel, copper, or molybdenum dithiocarbamates; and phosphosulfurizedolefins, e.g. phosphosulfurized pinene or styrene.

Corrosion Inhibitors and Metal Deactivators

Corrosion inhibitors which act by deactivating metal parts with whichthey come in contact and/or as sulfur scavengers can also be used in thecompositions or concentrates of the invention. Examples of such agentsinclude benzotriazole derivatives; thiadiazole compounds, e.g.2,5-dimercapto 1,3,4-thiadiazole; mercaptobenzothiazole compounds in theform of amine salts, sulphonamides, thiosulphonamides, and condensatesof mercaptobenzothiazole with amines and formaldehyde;salicylaldehyde/diamine condensation products; dialkylphosphites, e.g.dioleyl or di-2-ethylhexyl phosphite; trialkyl and triarylphosphites,e.g. tris-(2-ethyl-hexyl), triphenyl or tri(4-nonylphenol) phosphites;and thiophosphonates such as triphenyl or trilauryl thiophosphonate ortrilauryl tetrathiophosphonate.

Also useful are corrosion inhibitors based on aromatic sulfonic acidderivatives, for example derivative of a mono-, di-, or poly-alkylatednaphthalenesulfonic acid selected from the group consisting of:

(i) neutral metal salts of said mono-, di-, and poly-alkylatednaphthalenesulfonic acids;

(ii) basic metal salts of said mono-, di-, and poly-alkylatednaphthalenesulfonic acids;

(iii) amine salts of said mono-, di-, and poly-alkylatednaphthalenesulfonic acids; and

(iv) esters of said mono-, di-, and poly-alkylated naphthalenesulfonicacids; wherein the mono-, di-, and poly-alkylated naphthalenesulfonicacids are represented by formula

wherein R₅₁, R₅₂, R₅₃ and R₅₄ are individually selected from the groupconsisting of hydrogen or essentially linear hydrocarbyl groups havingabout 9 to about 22 carbon atoms; and wherein l, m, n and p are integersfrom 0 to 4 and the sum of l+m+n+p is at least 1; and wherein R₅₁, R₅₂,R₅₃ and R₅₄ is a hydrogen where either l, m, n, or p is 0.

One derivative of the alkylated naphthalenesulfonic acid composition isthe neutral metal salt component and is represented by the formula (II):

wherein R₅₁, R₅₂, R₅₃ and R₅₄, l, m, n and p are as defined above; M isa metal selected from the group consisting of alkali metals, alkalineearth metals, transition metals, Group IVb metals, and Group Vb metals;and x is the valence of M. M in formula (II) is an alkali metal selectedfrom the group consisting of lithium, sodium, potassium, and mixturesthereof. M may also be an alkaline earth metal selected from the groupconsisting of magnesium, calcium, strontium, barium and mixturesthereof. In other embodiments, M is a transition metal selected from thegroup consisting of zinc, copper, cerium, molybdenum, and mixturesthereof. In still other embodiments M may be a Group IVb metal andselected from the group consisting of tin, lead, and mixtures thereof. Mmay be a Group Vb metal selected from the group consisting of bismuth,antimony, and mixtures thereof.

The functional fluid composition may also contain at least onederivative of the alkylated naphthalenesulfonic acid composition that isthe overbased metal salt component described above and represented byformulae

and mixtures thereof wherein R₅₁, R₅₂, R₅₃ and R₅₄, l, m, n and p are asdefined earlier; M is a metal selected from the group consisting ofalkali metals, alkaline earth metals, transition metals, Group IVbmetals, and Group Vb metals; x is the valence of M; and z is 0.1 to 50.

The functional fluid composition contains one ammonium or organic aminesalt of formulae

wherein R₅₁, R₅₂, R₅₃ and R₅₄, l, m, n and p are as defined earlier andeach R₅₅ is individually selected from a hydrogen atom or a hydrocarbylgroup consisting of from 1 to 25 carbon atoms; and x is from 2 to 5.

The functional fluid composition contains at least one compoundrepresented by formula

wherein R₅₁, R₅₂, R₅₃ and R₅₄, l, m, n and p are as defined earlier andR₅₆ is a hydrocarbyl group consisting of from 2 to 18 carbon atoms.

Also useful are corrosion inhibitors based onN-acyl-N-hydrocarbonoxyalkyl aspartic acid compounds having the formula

wherein R⁶¹ is a hydrocarbonoxyalkyl group of from about 6 to about 30carbon atoms, R⁶² is a carboxyl substituted acyl group containing fromabout 2 to about 30 carbon atoms, or such a group at least partiallyneutralized with an alkali metal base, an alkaline earth metal base, anamine or a mixture of any of the foregoing, and R⁶⁴, R⁶⁵, R⁶⁶, and R⁶⁷are each, independently, selected from hydrogen or a hydrocarbon groupof from about 1 to about 30 carbon atoms.Friction Modifiers and Fuel Economy Agents

Friction modifiers and fuel economy agents, compatible with the otheringredients of the new compositions or concentrates may also beincluded. Examples of such materials are glyceryl monoesters and/ordiesters of higher fatty acids, e.g. glyceryl mono-oleate and esters oflong-chain polycarboxylic acids with diols, e.g. the butane diol esterof a dimerized unsaturated fatty acid, and oxazoline compounds.

Succinimides

Succinimides friction modifiers of the current invention may berepresented by the following general formula.

where R18 is a C6 to C30 isomerized alkenyl group, represented by:

(where g and h are integers whose sum is from 1 to 25), or its fullysaturated alkyl analog, R17 is an alkyl group, aryl group, and theirheteroatom containing derivatives.

The succinimides of the present invention are those produced fromsuccinic anhydrides substituted with isomerized alkenyl groups or theirfully saturated alkyl analogs. Preparation of the isomerized alkenylsuccinic anhydrides is described in, for example, U.S. Pat. No.3,382,172 hereby incorporated by reference in its entirety.

Often these materials are prepared by heating alpha-olefins with acidiccatalysts to migrate the double bond to form an internalolefin. Thismixture of olefins (2-enes, 3-enes, etc.) is then thermally reacted withmaleic anhydride. Typically olefins from C₆ (e.g. 1-hexene) to C₃₀ (e.g.1-tricosane) are used. Suitable isomerized alkenyl succinic anhydridesof structure (1)

include isodecylsuccinic anhydride (x+y=5), iso-dodecyisuccinicanhydride (x+y=), iso-tetradecylsuccinic anhydride (x+y=9),iso-hexadecylsuccinic anhydride (x+y=1), iso-octadecylsuccinic anhydride(x+y=13) and isoeicosylsuccinic anhydride (x+y=15). Preferred materialsare isohexadecylsuccinic anhydride and iso-octadecylsuccinic anhydride.

The materials produced by this process contain one double bond (alkenylgroup) in the alkyl chain. The alkenyl substituted succinic anhydridesmay be easily converted to their saturated alkyl analogs byhydrogenation.

Suitable primary and secondary amines useful to produce the succinimidesare represented by structure

where: R¹⁹ and R²⁰ are independently alkyl, aryl, their heteroatomcontaining derivatives, or H with the proviso that R¹⁹ and R²⁰ are notboth H. Preferred amines are n-hexylamine, di-n-hexylamine,dimethylamine, n-butylamine, diethanol amine anddi-methylaminopropylamine.

Bis succinimides of the current invention may be represented by thefollowing general formula

wherein R²¹ and R²² may be identical or different from each other andare each hydrocarbon groups having 5 or more carbons; R²³ is a divalenthydrocarbon group having 1 to 5 carbons; R²⁴ is a hydrogen atom or ahydrocarbon group having 1 to 20 carbons; and n is an integer in therange of 0 to 10

In the above general formula, R²¹ and R²² may be the same as each otheror different from each other, and are each saturated or unsaturatedhydrocarbon groups having 5 or more carbons, preferably 5 to 40 carbons.Examples of hydrocarbon groups include pentyl groups, hexyl groups,heptyl groups, octyl groups, nonyl groups, decyl groups, dodecyl groups,tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups,heptadecyl groups, octadecyl groups, nonadecyl groups, oleyl groups andother hydrocarbon groups having up to 40 carbons. Preferred hydrocarbongroups include straight chain hydrocarbon groups having between 8 and 25carbons. In the above general formula, R²³ is a divalent hydrocarbongroup having 1 to 5 carbons, preferably an alkylene group having 2 or 3carbons.

In the above general formula, R²⁴ is a hydrogen atom or a hydrocarbongroup having 1 to 20 carbons. Examples of hydrocarbon groups includealkyl groups having 1 to 20 carbons; alkenyl groups having 2 to 20carbons; cycloalkyl groups having 6 to 20 carbons; and aryl groupshaving 6 to 20 carbons. The aryl groups may have an alkyl group having 1to 12 carbons. Hydrogen atoms and alkyl groups having 1 to 10 carbonsare particularly preferred as R²⁴. Groups having a number of aminogroups and/or amide bonds in their structure (e.g. 1 to 5 of each) canbe used as the above-described hydrocarbon groups.

The amino groups are represented by —NH— or —NH₂; and the amide bondsare represented by

They may be bonded with the carbons of the hydrocarbon group at anarbitrary position.

The bis succinimides of the present invention are those produced fromsuccinic anhydrides substituted with isomerized alkenyl groups or theirfully saturated alkyl analogs, and polyamines. Suitable polyamines aresaturated amines of the general formula

where R²⁵, R²⁶, and R²⁷ are independently selected from the groupconsisting of H, C₁ to C₂₅ straight or branched chain alkyl radicals.,C₁ to C₁₂ alkoxy radicals; C₂ to C₆ alkylene radicals; u is an integerfrom 1 to 6, preferably 2 to 4; and v is an integer from 0 to 10,preferably from 1 to 4.

Non-limiting examples of suitable polyamine compounds include:1,6-diaminohexane, diethylene triamine, triethylene tetramine,tetraethylene pentamine, and pentaethylene hexamine. Useful mixtures ofpolyamines having from 5 to 7 nitrogen atoms per molecule are availablefrom Dow Chemical Co. as Polyamine H, Polyamine 400 and Polyamine E-300.

Polyoxyalkylene amines are also useful in this invention and are shownas structureH₂N-alkylene-(-O-alkylene-)u ₁-NH₂where u₁ is an integer of from 1 to 10. The polyamines have molecularweights from about 100 to 500. The preferred polyoxyalkylene polyaminesinclude polyoxyethylene and polyoxypropylene diamines and thepolyoxypropylene triamines. Commercial polyoxyalkylene amines areavailable from Jefferson Chemical Co. sold under the trade name“Jeffamines® D-230, D-400, D-1 000, T-430,” etc.

In preferred embodiments, the alkenyl succinic anhydride startingmaterials for forming the friction modifiers of above structure can beeither of two types. The two types differ in the linkage of the alkylside chain to the succinic acid moiety. In the first type, the alkylgroup is joined through a primary carbon atom in the starting olefin,and therefore the carbon atom adjacent to the succinic acid moiety is asecondary carbon atom. In the second type, the linkage is made through asecondary carbon atom in the starting olefin and these materialsaccordingly have a branched or isomerized side chain. The carbon atomadjacent to the succinic acid moiety therefore is necessarily a tertiarycarbon atom.

The alkenyl succinic anhydrides of the first type, shown below, withlinkages through secondary carbon atoms, are prepared simply by heatingα-olefins, that is, terminally unsaturated olefins, with maleicanhydride. Non-limiting examples of these materials include n-decenylsuccinic anhydride, tetradecenyl succinic anhydride, n-octadecenylsuccinic anhydride, tetrapropenyl succinic anhydride, poly butenylsuccinic anhydrides, etc.

wherein R⁷⁸ is C₂ to C₃₇ alkyl.

A second type of alkenyl succinic anhydrides, with linkage throughtertiary carbon atoms, is produced from internally unsaturated olefinsand maleic anhydride. Internal olefins are olefins which are notterminally unsaturated, and therefore do not contain the

moiety. These internal olefins can be introduced into the reactionmixture as such, or they can be produced in situ by exposing α.-olefinsto isomerization catalysts at high temperatures. A process for producingsuch materials is described in U.S. Pat. No. 3,382,172 herebyincorporated by reference in its entirety. The isomerized alkenylsubstituted succinic anhydrides are compounds having structure

where x and y are independent integers whose sum is from 1 to 35.

The preferred succinic anhydrides are produced from isomerization oflinear α-olefins with an acidic catalyst followed by reaction withmaleic anhydride. The preferred α-olefins are 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosane, ormixtures of these materials. The products described can also be producedfrom internal olefins of the same carbon numbers, 8 to 20. The preferredmaterials for this invention are those made from 1-tetradecene (x+y=9),1-hexadecene (x+y=11), 1-octadecene (x+y=13), 1-didodecene (x+y=15), and1-tetradidodecene (x+y=19) or mixtures thereof.

The preferred succinimide friction modifiers of this invention areproducts produced by the reaction of isomerized alkenyl succinicanhydride with diethylene triamine, triethylene tetramine, tetraethylenepentamine or mixtures thereof. The most preferred products are preparedusing diethylene triamine, triethylene tetramine, and tetraethylenepentamine. The alkenyl succinic anhydrides are typically reacted withthe amines in a 2:1 molar ratio so that both primary amines areconverted to succinimides. Sometimes a slight excess of isomerizedalkenyl succinic anhydride is used to insure that all primary amineshave reacted.

The two types of succinimide friction modifiers can be used individuallyor in combination.

The disuccinimides may be post-treated or further processed by anynumber of techniques known in the art. These techniques would include,but are not limited to, boration, maleation, and acid treating withinorganic acids such as phosphoric acid, phosphorous acid, and sulfuricacid. Descriptions of these processes can be found in, for example, U.S.Pat. Nos. 3,254,025; 3,502,677; 4,686,054; and 4,857,214 herebyincorporated by reference in their entirety.

Other useful derivatives of the succinimide modifiers are where thealkenyl groups of above structures have been hydrogenated to form theirsaturated alkyl analogs. Saturation of the condensation products ofolefins and maleic anhydride may be accomplished before or afterreaction with the amine. These saturated versions of above structuresmay likewise be post-treated as previously described.

While any effective amount of the compounds of above structure and itsderivatives may be used to achieve the benefits of this invention,typically these effective amounts will range from 0.01 to 10 weightpercent of the finished fluid, preferably from 0.05 to 7 weight percent,most preferably from 0.1 to 5 weight percent.

Viscosity Index Improvers

Viscosity index improvers or viscosity modifiers are typically polymersof number average molecular weight 103 to 106—for example ethylenecopolymers or polybutenes. Viscosity index improvers may be modified tohave dispersant properties and suitable viscosity index improverdispersants for use in compositions of the invention are described in,for example, EP 24 146 A and are as follows:

(a) polymers comprising monomer units derived from a C₄ to C₂₄unsaturated ester of vinyl alcohol or a C₃ to C₁₀ unsaturated mono- ordicarboxylic acid and an unsaturated nitrogen-containing monomer having4 to 20 carbon atoms;

(b) polymers comprising monomer units derived from a C₄ to C₂₀ olefinand an unsaturated C₃ to C₁₀ mono- or dicarboxylic acid neutralized withan amine, a hydroxyamine or an alcohol; and

(c) polymers of ethylene with a C₃ to C₂₀ olefin further reacted bygrafting a C₄ to C₂₀ nitrogen-containing monomer thereon or by graftingan unsaturated acid onto the polymer backbone and then reacting thecarboxylic acid groups with an amine, hydroxy amine, or alcohol. (Otheradditives which may be used in accordance with the present invention aredescribed in EP24146A). These viscosity index improvers also havedispersant properties, as is preferred in accordance with the invention,although viscosity index improvers without dispersant properties may beused if desired.

Preferred viscosity index improvers with dispersant properties for usein the compositions of the present invention comprise a polyolefinmoiety to which is grafted an unsaturated carboxylic acid moiety, thecarboxylic acid groups being reacted with an amine, hydroxyamine oralcohol.

Antioxidants may be evaluated using the sequence III E test (ASTM STP315) which is a standard test used for assessing the oxidationresistance of lubricants and which is a more stringent version of thesequence III D test (ASTM STP 315M and ASTM STP 315). The sequence IIImethod produces a result after 64 hrs of testing with an acceptableperformance being a 375% or less increase in kinematic viscosity asmeasured at 40° C. after this period. The principle of this method is toobserve oil thickening as a result of oxidation. When evaluatingantioxidants for lubricants it is desirable to be able to use screeningtest methods which are quicker and easier to use than the Sequence IIItest. One such method which is commonly used is a thin film hightemperature catalytic oxidation test performed using a DSC.

The invention will be further illustrated by means of the followingexamples. The following examples illustrate the invention and are not tobe used to limit the scope of the invention.

Preparation of Amine Tungstates from Tungstic Acid (Method A)

A mixture of the starting amine (2 eq.), tungstic acid (1 eq.),dissolved in aqueous ammonia was stirred at 95-1100 C for 2-3 hrs, andwater and excess ammonia were then removed by distillation followed bythe isolation of the product as viscous liquid.

Preparation of Amine Tungstates from Ammonium Para Tungstate (Method B)

A mixture of the starting amine (26 eq.) and aqueous ammoniumparatungstate (1 eq.) was heated with vigorous mixing. Water and excessammonia were then removed by distillation followed by the isolation ofthe product as viscous liquid.

Preparation of Amine Tungstates from Metal Tungstates (Method C)

Tungstic acid can also be prepared from an appropriate metal tungstateand sulfuric acid. The reaction of tungstic acid (1 eq.) with theappropriate amine (2 eq.) can be conducted in a hydrocarbon solvent atelevated temperatures, to yield the desired amine tungstate product.

Preparation of Amine Tungstates from Metal Tungstates and QuaternaryAmmonium Halides or Sulfates (Method D)

The amine tungstates can also be prepared by the reaction of quaternaryammonium halides or sulfates, in heptane with sodium or potassiumtungstate in water. Method Physical Example Starting amine Used Form % W1 Primene JMT(C₁₆-C₂₂ tert-alkyl primary A Yellow 18.7 aliphatic amine)Liquid 2 Primene JMT(C₁₆-C₂₂ tert-alkyl primary B Yellow 19.5 aliphaticamine) Liquid 3 Primene JMT(C₁₆-C₂₂ tert-alkyl primary C Yellow 11aliphatic amine) Liquid 4 Primene JMT(C₁₆-C₂₂ tert-alkyl primary CYellow 32.6 aliphatic amine) (tungstic Liquid acid:amine 1:1) 5 PrimeneJMT(C₁₆-C₂₂ tert-alkyl primary D Yellow 34 aliphatic amine) viscousLiquid 6 Primene 81R(C12-C14 tert-alkyl primary A White waxy 18aliphatic amine amine) solid 7 Di(tridecyl) amine A Yellow 9.1 liquid 8Di(tridecyl) amine B Yellow 15.0 liquid 9 Di(tridecyl) amine C Yellow28.4 liquid 10 Salt of N-oleyl-1,3-propanediamine B Blue-Green 8.9(Duomeen OL), with Dinonyl naphthalene Liquid sulfonic acid 11 Salt ofN-oleyl-1,3-propanediamine B Blue-Green 8.3 (Duomeen OL), with Didodecylnaphthalene Liquid sulfonic acid 12 Salt of N-oleyl-1,3-propanediamine BYellow 13.8 (Duomeen OL), with Naphthenic acid Liquid 13 Reactionproduct of Canola Oil with N- B Yellow 9.6 oleyl-1,3-propanediamine(Duomeen OL) Liquid 14 Reaction product of aminoethyl imidazoline CYellow 8.0 with Didodecyl naphthalene sulfonic acid Liquid 15 Bissuccinimide from alkenyl succinic B Yellow 2.5 anhydride and diethylenetriamine Liquid 16 Bis(2-hydroxyethyl)cocoalkylamine B Yellow 17.4Liquid 17 Alkyl (C14-C18) bis(2-hydroxyethyl) B Yellow 5.7 amine Liquid18 Alkyl (C14-C18) bis(2-hydroxyethyl) B Yellow 7.9 amine Liquid 19 Saltof N-oleyl-1,3- B Yellow 7.4 propanediamine(Duomeen OL), with Di(2-Liquid ethylhexyl) phosphonic acid 20 Salt of N-oleyl-1,3- B Brown 10.9propanediamine(Duomeen OL), with Di(2- Liquid ethylhexyl)dithiophosphoric acid 21 Bis succinimide from alkenyl succinic C Yellow8.3 anhydride and diethylene triamine Liquid 22 Salt of N-oleyl-1,3- BYellow propanediamine(Duomeen OL), with Liquid dioleyl phosphonic acidPreparation of New Amine Molybdates

A solution of starting amine (2 eq.), in heptane was combined withMolybdenum trioxide (1 eq.) in water and the resulting mixture washeated under reflux for 4-6 hrs. Water was removed by azeotropicdistillation, under reduced pressure, resulting in the desired aminemolybdates as a viscous oily product.

Another method involved the reaction of sodium molybdate (1 eq.) inwater with amine (2 eq.) at 60-70° C., for 1 hr., followed by theaddition of 1 eq., of aqueous sulfuric acid. The aqueous layer wasseparated and the organic residue was dehydrated under reduced pressureresulting in the desired molybdate as a viscous oily product.

Yet another method involved the reaction of ammonium molybdate (1 eq.),with amine (2 eq.) in refluxing toluene, and removing watercontinuously. The molybdate was isolated as a viscous liquid. Molysource Physical Example Starting amine Used Form % Mo 23 Salt ofN-oleyl-1,3-propanediamine (Duomeen MoO₃ Brown 5.37 OL), with Dinonylnaphthalene sulfonic acid Liquid 24 Salt of N-oleyl-1,3-propanediamine(Duomeen MoO₃ Viscous 4.1 OL), with Naphthenic acid Yellow Liquid 25Salt of N-oleyl-1,3-propanediamine(Duomeen MoO₃ Yellow 4.2 OL), withDi(2-ethylhexyl) phosphoric acid Liquid 26 Bis succinimide from alkenylsuccinic MoO₃ Viscous 2.6 anhydride and diethylene triamine Green Liquid27 Salt of N-oleyl-1,3-propanediamine(Duomeen MoO₃ Brown 6.3 OL), withDi(2-ethylhexyl) dithiophosphoric Liquid acidTest for Oxidation Induction Time by Pressure Differential ScanningCalorimetry (PDSC)

The Pressure Differential Scanning Calorimetry (PDSC) test method is athin film high temperature catalytic oxidation test, for determinationof oxidation induction time (OIT). The procedure used for this analysiswas ASTM 6186-03. In the test, the compounds to be evaluated forantioxidancy performance were added at the required treat rate to asample of Chevron Group II ISOVG 46 base oil containing no otheradditive. This test sample (6-9 mg) was placed in the center of analuminum DSC pan and inserted into a DuPont 910 High Pressure DSC,equipped with a pressure cell and interfaced to a TA Instruments 2000thermal analysis controller. The pressure cell of the DSC was closed,purged with O₂, equilibrated at 70° C., and heated to 210° C. at a rateof 40° C./min. When the temperature had reached 209° C. the cell waspressurized with oxygen to a pressure of 500 psi and the cell held at210° C. After a period of time the test sample underwent an exothermicoxidative reaction; this event and magnitude of the associated heateffects compared to the inert reference were monitored and recorded. Thedata obtained was analyzed using TA Instruments Universal Analysisprogram V4.1D. The oxidation induction time (OIT; time toauto-oxidation) is the time at which the baseline intersects with a linetangent to the curve of the exothermal heat flow versus time scan. TheOIT is reported in minutes. The magnitude of the OIT is an indication ofthe effectiveness of the compounds or compound mixtures under test asantioxidants; the larger the OIT the greater the antioxidant effect.Oxidation induction time Sample (minutes) 0.5% amine tungstate of Ex. 10 0.5% NA-LUBE AO142(Octyl/butyldiphenyl amine) 2.8 0.5% NA-LUBEAO142(Octyl/butyldiphenyl amine) + 12.0 900 ppm amine tungstate of Ex. 1Clearly the amine tungstates of the current invention providedsynergistic antioxidant activity, in combination with aminicantioxidants. Synergistic antioxidant effects of combining aminetungstate compounds of the current invention with an aminic antioxidantwere noted with a larger OIT for these combinations.Oxidative Stability by Rotating Pressure Vessell Oxidation Test (RPVOT)

Also thermo-oxidative stability of these synergistic mixtures incombination with Group II base oil at various concentrations weredetermined using the ASTM D 2272 Rotating Pressure Vessell OxidationTest (RPVOT) method.

The RPVOT test utilizes an oxygen-pressure bomb to evaluate theoxidation stability of oils in the presence of water and a coppercatalyst coil at 150° C. The test oil, water and a copper catalyst coil,contained in a covered glass container, were placed in a vessel equippedwith a pressure gauge. The bomb was charged with oxygen to a pressure of90 psi, placed in a constant temperature oil bath at 150° C., androtated axially at 100 rpm at an angle of 30° from the horizontal. Thetime period required for the pressure to drop to 25 psi is the measureof the oxidation stability of the test sample: the longer the time, thebetter the oxidative stability of the material. Sample in Chevron ISO VG46 base Oil W(ppm) RPVOT minutes No additive 38 0.5% NA-LUBE ®AO142(Octyl/butyldiphenyl amine) — 313 0.5% NA-LUBE ®AO142(Octyl/butyldiphenyl amine) + amine 142 1359 tungstate of Ex. 100.5% NA-LUBE ® AO142(Octyl/butyldiphenyl amine) + amine 133 1274tungstate of Ex. 11 0.5% NA-LUBE ® AO142(Octyl/butyldiphenyl amine) +amine 139 918 tungstate of Ex. 16 0.5% NA-LUBE ®AO142(Octyl/butyldiphenyl amine) + amine 143 1202 tungstate of Ex. 170.5% NA-LUBE ® AO142(Octyl/butyldiphenyl amine) + amine 145 1163tungstate of Ex. 15 0.5% NA-LUBE ® AO142(Octyl/butyldiphenyl amine) +amine 142 1170 tungstate of Ex. 18 0.5% NA-LUBE ®AO142(Octyl/butyldiphenyl amine) + amine 142 828 tungstate of Ex. 8 0.5%NA-LUBE ® AO142(Octyl/butyldiphenyl amine) + amine 142 532 tungstate ofEx. 9 0.5% NA-LUBE ® AO142(Octyl/butyldiphenyl amine) + amine 142 801tungstate of Ex. 5 0.5% NA-LUBE AO142(Octyl/butyldiphenyl amine) + amine140 1023 tungstate of Ex. 12 0.5% NA-LUBE AO142(Octyl/butyldiphenylamine) + amine 140 1790 tungstate of Ex. 14 0.5% NA-LUBEAO142(Octyl/butyldiphenyl amine) + amine 140 636 tungstate of Ex. 13

Synergistic antioxidant effects of combining amine tungstate compoundsof the current invention with an aminic antioxidant were once againnoted with a larger induction time for these combinations. RPVOT Samplein Chevron ISO VG 46 base Oil W(ppm) minutes No additive 38 Aminetungstate of Ex. 1 144 32 0.5% NA-LUBE ® AO142(Octyl/butyldiphenyl — 313amine) 0.5% NA-LUBE ® AO142(Octyl/butyldiphenyl 144 865 amine) + aminetungstate of Ex. 1 0.7% ZDDP(Zinc dialkyldithiophosphate) — 130 0.7%ZDDP(Zinc dialkyldithiophosphate) + amine 144 488 tungstate of Ex. 1

Synergistic antioxidant effects of combining amine tungstate compoundsof the current invention with an aminic antioxidant, and a dialkyldithiophosphate were once again noted with a larger induction time forthese combinations.

Friction Performance

The friction coefficients of compounds of current invention wereevaluated in prototype motor oil using a modified ASTM D5707 SRV Ball onPlate protocol; 400N, 50 Hz; 1.00 mm stroke 120° C.; 120 min. The datashowed an improvement in friction coefficient for compounds of currentinvention compared to the base oil with no friction modifier additive.Sample in Chevron ISO VG 46 base Oil, containing ashlessdithiophosphate, ZDDP, Final friction triphenylphosphate ester, andalkylated coefficient) after naphthalene sulfonate rust inhibitor W(ppm)120 min.) No additive — 0.103 Ex. 8 142 0.069 Ex. 5 142 0.065 Ex. 9 1420.085 Ex. 1 144 0.061 Ex. 2 142 0.062 Ex. 10 142 0.076 Ex. 18 142 0.070Ex. 11 142 0.079 Ex. 12 142 0.079 Ex. 13 451 0.071 Ex. 14 448 0.078 Ex.17 143 0.080 Ex. 19 500 0.061

Sample in Exxon Final friction coefficient) Superflo 10w-30 oil Mo(ppm)after 120 min.) No additive — 0.135 Molyvan 855 800 0.054 Ex. 23 5370.053 Ex. 24 520 0.057 Ex. 25 521 0.063 Ex. 26 520 0.054

1. A lubricating oil additive composition comprising lubricating oil inan amount greater than 50% by weight; an oil soluble secondary diarylamine, and/or an oil soluble alkylated phenothiazine; and an oil solubleor oil dispersible tungsten compound wherein the oil soluble or oildispersible tungsten compound comprises an organo tungstate or an aminetungstate derived from amines selected from the group consisting of: (a)a primary amine of the formula:

wherein R¹, R², and R³ are independently hydrogen, C₁-C₂₅ alkyl, C₂-C₂₅alkyl interrupted by oxygen or sulfur; C₂-C₂₄ alkenyl, C₄-C₁₅ cycloalkylwhich is unsubstituted or substituted by C₁-C₄ allyl and/or carboxyl;C₅-C₁₅ cycloalkenyl which is unsubstituted or substituted by C₁-C₄ alkyland/or carboxyl; C₁₃-C₂₆ polycycloalkyl, C₇-C₉ phenylalkyl which isunsubstituted or substituted on the phenyl ring by C₁-C₄ alkyl; —COR₆, a5- or 6-membered heterocyclic ring which is unsubstituted or substitutedby C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; a 5- or 6-memberedheterocyclic ring which is benzo-fused and is unsubstituted orsubstituted by C₁-C₄ alkyl, C₁-C₄ alkoxy, halogen or carboxyl; (b) asecondary amine of the formula:

wherein R⁴ and R⁵ are independently hydrogen, linear, branched,saturated or unsaturated alkyl of 1 to 40 carbon atoms, cycloalkyl of 5to 40 carbon atoms, aryl of 6 to 40 carbon atoms, aralkyl of 7 to 9carbon atoms, where the aralkyl is substituted further by alkyl of 1 to36 carbon atoms; (c) a tertiary amine of the formula:

wherein R₁, R₂, and R₃ are independently each a C₁ to C₃₆ residue thatmay optionally contain at least one —O—, —S—, —SO—, —CO₂—, —CO—, or—CON— moiety, cycloalkyl of 5 to 12 carbon atoms, aralkyl of 7 to 9carbon atoms, where the aralkyl is further substituted by alkyl of 1 to36 carbon atoms; (d) a polyamine of the formula:

wherein R₇, R₈ and R⁹ are each hydrogen; C₁ to C₂₅ straight or branchedchain alkyl radicals; C₁ to C₁₂ alkoxy-(C₆ alkylene) radicals; C₂ to C₁₂alkylamino-C₂ to C₆ alkylene) radicals; each s can be the same or adifferent number of from 2 to 6, and t is a number from 0 to 10, and atleast one of R₇, R₈ and R₉ is hydrogen; (e) an N-aminoalkyl piperazineof the formula:

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3; (f) an imidazoline of the formula:

in which n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, or substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, aryl, aralkyl, cycloalkyl or heterocyclic radical, optionallysubstituted with halogen, nitro groups, alkyl groups, alkoxy groups oramino groups, and, when m=1 represents hydrogen. (g) a sulfur containingamine, or an organotungstate containing sulfur of the followingstructure:

where R⁶ and R⁷ are independently the same or different and are selectedfrom H and C₁ to C₃₀ and are an alkyl group, a cycloalkyl group, an arylgroup or an alkaryl group, with the proviso that at least one of R⁶ orR⁷ is H for at least one of the thiocarbamate groups, and at least oneof R⁶ or R⁷ is hydrocarbyl for each of the thiocarbamate groups, M is W,X is O or S, b₁ is at least 1, a₁ is at least 1 depending on theoxidation state of M, c₁ is at least 1 depending on the oxidation stateof M and d₁ is 0 or at least 1 depending on the oxidation state of M;(h) a sulfurized oxymetal organophosphorodithioates with the structure:

wherein M is tungsten, R⁸ and R⁹ may be the same or different, each ofR⁸ and R⁹ contains from 1 to 30 carbon atoms and are selected from thegroup consisting of an alkyl group, a cycloalkyl group, an aryl group,and a alkylaryl group; and x₁ and y₁ are positive real numberssatisfying the equation: x₁+y₁=4; (i) an aminosilane of the formula:

wherein R₁₇ and R₁₈ independently hydrogen, C₁-C₂₅ alkyl,2-hydroxyethyl, C₃-C₂₅ alkyl which is interrupted by oxygen or sulfur;C₂-C₂₄ alkenyl or

R₁₉ is C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen orsulfur; hydroxyl, C₁-C₁₈ alkoxy or C₂-C₂₄ alkenyl, R₂₀ is hydroxyl,C₁-C₁₈ alkoxy or C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur;and, if a and b together are 1, three radicals R₂₀ together are N(CH₂CH₂O—)₃, X₂ is C₁-C₁₈ alkylene, C₂-C₂₀ alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈ cycloalkylene, phenylene or naphthylene which isunsubstituted or substituted by C₁-C₄ alkyl; or is C₄-C₁₈ alkylene whichis interrupted by oxygen, sulfur or

R₂₁ is hydrogen or C₁-C₈ alkyl with the proviso that two nitrogen atomsare not attached to the same carbon atom, a is 1 or 2, and b is 0, 1 or2; (j) an ethoxylated amine of formula:

where Z is straight or branched chain alkyl of from about 8 to about 26carbon atoms, alkoxy alkyl of 4 to 22 carbon atoms and n=2 to about 50,and x₁=from about 1 to about 49; (k) an alkylated phenothiazine of theformula:

wherein R₁₁ and R₁₂ are hydrogen or together form a fused six-memberedaromatic ring, one of R₁₃ and R₁₄ is hydrogen and the other is C₂-C₃₀alkyl, cyclo-C₅-C₁₂ alkyl, C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl orα,α-dimethylbenzyl; or both R₁₃ and R₁₄ are C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ hydrogen; or R₁₃ is hydrogen and R₁₄ is C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ together form a fused six-membered aromatic ring, R₁₅ is hydrogen,C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or a group —CH₂SR₄, whereR₄ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or an alkylene, aralkylenebridging two phenothiazine moieties; (l) an alkylated diarylamine of theformula:

wherein R₂₂ and R₂₃ each independently represents a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms, R₂₄ ishydrogen, C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or a group—CH₂SR₅, where R₅ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or analkylene, aralkylene bridging two amine moieties; (m) a triazole of theformula:

wherein R₂₅ is hydrogen or a C₁-C₂₀ alkyl residue, R₂₆ and R₂₇ are thesame or different and each is H, C₁-C₂₀ alkyl, C₃-C₂₀ alkenyl, C₅-C₁₂cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆ and R₂₇, together withthe nitrogen atom to which they are attached, form a 5-, 6- or7-membered heterocyclic residue or R₂₆ and R₂₇ is each a residue offormula:R₂₈X₃[(alkylene)O]_(n1)(alkylene)- wherein X₃ is O, S or N(R₂₈), R₂₈ ishydrogen or C₁-C₂₀ alkyl, “alkylene” is a C₁-C₁₂ alkylene residue and n₁is 0 or an integer from 1 to 6, R₃₀ is hydrogen, C₁-C₂₀ alkyl or C₆-C₁₀aryl or C₇-C₁₈ alkyl phenyl; and R₃₁ is hydrogen, C₁-C₂₀ alkyl or aresidue —CH₂ NR₂₆R₂₇ wherein R₂₆ and R₂₇ have their previoussignificance or R₂₆ has its previous significance and R₂₇ is a residueof formula:

or R₂₇ is a residue of formula as defined above and R₂₆ is a residue offormula:-[alkylene]_(n1)-N(R₃₂)_A₋[N(R₃₂)₂]_(m1) wherein m₁ is 0 or 1 and, whenm₁ is 0, A is a residue of formula (I) and, when m₁ is 1, A is alkyleneor C₆-C₁₀ arylene, and alkylene and n₁ have their previous significanceand R₃₂ is a residue of formula I, as defined above; (n) a substitutedphenol of the formula:

wherein R₄₁, and R₄₂ are independently alkyl of 1 to 18 carbon atoms,cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alkylof 1 to 18 carbon atoms, aralkyl of 7 to 9 carbon atoms or said aralkylsubstituted by alkyl of 1 to 18 carbon atoms, R₂₆ and R₂₇ are the sameor different and each is H, C₁-C₂₀ alkyl, C₃-C₂₀ alkenyl, C₅-C₁₂cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆ and R₂₇, together withthe nitrogen atom to which they are attached, form a 5-, 6- or7-membered heterocyclic residue or R₂₆ and R₂₇ is each a residue offormula:R₂₈X₃[(alkylene)O]_(n1)(alkylene)- wherein X₃ is O, S or N(R₂₈), R₂₈ ishydrogen or C₁-C₂₀ alkyl, “alkylene” is a C₁-C₁₂ alkylene residue and n₁is 0 or an integer from 1 to 6; o) a polyamine salt derived from thereaction of a polyamine and an acid; wherein said polyamine is selectedfrom the group consisting of 1) polyamine with the following formula

where x is 1 or 2, and R is an aromatic or aliphatichydrocarbon-containing group containing a minimum of about 6-24 carbonatoms, wherein R optionally may also contain oxygen; 2) a polyamine ofthe formula

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3; and 3) a polyamine of the formula

wherein n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, or substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, an aryl, aralkyl, cycloalkyl or heterocyclic radical,substituted if desired with halogen, nitro groups, alkyl groups, alkoxygroups or amino groups, and, when m=1, represents hydrogen; and  andsaid acid is selected from the group consisting of 1) alkylatedmonosulfonic acid, of the formula

wherein R¹⁰ is H or an alkyl group containing up to 20 carbon atoms, andx is an integer from 0 to 2; 2) an alkylated aryl sulfonic acid of theformula

wherein R₅₁, R₅₂, R₅₃ and R₅₄ are individually selected from the groupconsisting of hydrogen or essentially linear hydrocarbyl groups havingabout 9 to about 22 carbon atoms; and wherein l, m, n and p are integersfrom 0 to 4 and the sum of l+m+n+p is at least 1; and wherein R₅₁, R₅₂,R₅₃ and R₅₄ is a hydrogen where either l, m, n, or p is 0; 3) alkylatedaryl disulfonic acids of the formula

wherein each of R¹¹ and R¹² is the same or different and is a linear orbranched alkyl group with 6 to 16 carbons, y is 0 to 3, z is 0 to 3 withthe proviso that y+z is 1 to 4, n is 0 to 3, B is a divalent moietyselected from the group consisting of —C(R¹³)(R¹⁴)—, wherein each of R¹³and R¹⁴ is H or independently a linear or branched alkyl group of 1-4carbons and n is 1; —C(═O)—, wherein n is 1; —O— wherein n is 1; —S—,wherein n is 1 to 3; and —SO₂—, wherein n is 1; 4) a mixture ofnaphthenic acids, wherein said mixture of napthenic acids comprises amixture of monobasic acids of cycloparaffins derived from eithercyclopentane or cyclohexane and cyclopentane and homologs and highermolecular weight analogs, said napthenic acids having molecular weightsfrom about 180 to about 350; 5) dihydrocarbylphosphoric acids,dihydrocarbyldithiophosphoric acids, or dihydrocarbylmonothiophosphoricacids of the formula

wherein Y₁ and Y₂ are each independently S or O and wherein R¹⁵ and R¹⁶are each independently H, C₃-C₁₈ alkyl, C₅-C₁₂ cycloalkyl, C₅-C₆cycloalkylmethyl, C₉-C₁₀ bicycloalkylmethyl, C₉-C₁₀ tricycloalkylmethyl,phenyl, C₇-C₂₄-alkylphenyl, i-propyl, i-butyl, 2-ethylhexyl, octylphenyl or oleyl or R¹⁵ and R¹⁶ together form a group of the partialformula,

a C₉-C₁₀ bicycloalkylmethyl, or a C₉-C₁₀ tricycloalkylmethyl are of theformulae:

6) an alkyl phenoxyalkanoic acid of the formula

wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

7) an N-acyl sarcosine of the formula

wherein the acyl group R^(t)—C(═O)— is the residue of a fatty acidhaving 10 to 20 carbon atoms. 8) a long-chain monocarboxylic acidcontaining 8-100 carbon atoms; p) a reaction product of a long chainmonocarboxylic acid, naphthenic acid, alkyl phenoxy alkanoic acid,N-acyl sarcosine or fatty oil, with a diamine, wherein the fatty oil isa triglyceride of the following formula:

where R, R′ and R″ independently represent saturated or unsaturatedaliphatic hydrocarbon groups having from about 8 to about 22 carbonatoms, wherein an alkyl phenoxyalkanoic acid is of the formula

wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

wherein an N-acyl sarcosine is of the formula

wherein the acyl group R^(t)—C(═O)— is the residue of a fatty acidhaving 10 to 20 carbon atoms; wherein the long-chain monocarboxylic acidcomprises 8-100 carbon atoms; wherein a mixture of naphthenic acids,comprises a mixture of monobasic acids of cycloparaffins derived fromeither cyclopentane or cyclohexane and cyclopentane and homologs andhigher molecular weight analogs, said napthenic acids having molecularweights from about 180 to about 350; and wherein the diamine has thefollowing formula:

where x is 1 or 2, and R is an aliphatic or aromatichydrocarbon-containing group containing a minimum of about 6-24 carbonatoms, which optionally may also contain oxygen; q) a reaction productof substituted succinic anhydrides with a polyamine, wherein saidreaction product has the formula

wherein R¹⁸ is a C6 to C30 isomerized alkenyl group, represented by:

(where g and h are integers whose sum is from 1 to 25), or its fullysaturated alkyl analog, R¹⁷ is an alkylamine group, arylamine group, andtheir heteroatom containing derivatives; or said reaction product hasthe formula

wherein, R²¹ and R²² may be identical or different from each other andare each saturated or unsaturated hydrocarbon groups having 5 to 40carbons; R²³ is a divalent hydrocarbon group having 1 to 5 carbons; R²⁴is a hydrogen atom or a hydrocarbon group having 1 to 20 carbons,wherein the hydrocarbon groups contain from 1 to 5 of each amine and/oramide substituted alkyl groups and n is an integer in the range of 0 to10.
 2. The lubricating oil composition as described in claim 1, whereinthe diaryl amine comprises an alkylated diphenyl amine.
 3. Thelubricating oil composition as described in claim 1, wherein thealkylated diarylamine has a concentration of about 0.075 to 2.5 wt. % inthe lubricating composition.
 4. The composition of claim 1 wherein thediaryl amine is of the formula

wherein R₂₂ and R₂₃ each independently represents a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms.
 5. Thelubricating oil composition as described in claim 3, wherein thealkylated diarylamine has a concentration of about 0.1 to 0.5 wt. % inthe lubricating composition.
 6. The composition as described in claim 4wherein at least one of the aryl groups is alkaryl having from 7 to 20carbon atoms in the alkyl group.
 7. The composition as described inclaim 2 wherein the alkylated diphenylamine is of the formula:

wherein D₁ and D₂ may be the same or different and each independentlyrepresents a hydrocarbyl radical of 1 to 28 carbon atoms. E and F may bethe same or different and may equal 0, 1, 2 or
 3. 8. The lubricating oilcomposition as described in claim 1, wherein the diaryl amine comprisesoil soluble alkylated phenothiazine.
 9. The lubricating oil compositionas described in claim 8, wherein the oil soluble alkylated phenothiazinehas a concentration of about 0.05 to 1.5 wt %.
 10. The lubricatingcomposition as described in claim 1, wherein at least one of the alkylgroups of the alkylated phenothiazine comprises from 4 to about 24carbon atoms.
 11. The lubricating oil composition as described in claim1, wherein the oil soluble tungsten compound is present in an amountsufficient to provide about 20 to 4000 ppm of tungsten in thelubricating composition.
 12. The lubricating oil composition asdescribed in claim 11, wherein the oil soluble tungsten compound ispresent in an amount sufficient to provide about 20 to 1000 ppm oftungsten in the lubricating composition.
 13. The lubricating oilcomposition as described in claim 1, wherein the antioxidant is selectedfrom the group consisting of copper-containing antioxidants, sulfurcontaining antioxidants, phenolic antioxidants, and mixtures thereof.14. The lubricating oil as described in claim 13 wherein the copper saltis selected from the group of carboxylates consisting of naphthenates,oleates, stearates, dialkyldithiophosphates, dialkyldithiocarbamates andmixtures thereof.
 15. The lubricating oil composition as described inclaim 1 wherein at least one of the following additives is present: adispersant, a detergent, a friction modifier, an antiwear additive, acorrosion inhibitor, a metal deactivator, a fuel economy agent, and aviscosity index improver.
 16. The lubricating oil composition as claimedin claim 15, wherein said lubricating oil composition comprises a baseoil, at least one antioxidant, a zinc dialkyldithiophosphate and atleast one organotungsten compound in an amount sufficient to provide thecomposition with about 20 to about 4000 ppm of tungsten.
 17. A methodfor making a lubricating oil composition comprising, said methodcomprising combining an oil of lubricating viscosity with at least oneantioxidant and at least one organotungsten compound in an amountsufficient to provide the composition with about 20 to about 4000 ppm oftungsten.
 18. A lubricating oil composition prepared according to themethod of claim
 17. 19. The method of claim 17 wherein the antioxidantis selected from the group consisting of alkylated diaryl amineantioxidants, alkylated phenothiazine antioxidants, phenolicantioxidants, sulfur-containing antioxidants, copper-containingantioxidants, and mixtures thereof.
 20. A method for lubricating aninternal combustion engine comprising treating moving parts of aninternal combustion engine with a lubricating oil additive compositionof claim 1, wherein said lubricating oil additive composition comprisesat least one organotungsten compound in an amount sufficient to providesaid lubricating oil additive composition with 20-4000 ppm of tungstenand at least one antioxidant.
 21. A method for improving theantioxidancy and/or anti-wear properties of a lubricating compositioncomprising adding to the lubricant composition an oil soluble tungstencompound, and an oil soluble diaryl amine and/or an oil solublealkylated phenothiazine.
 22. The method as described in claim 21,wherein the secondary diarylamine is an alkylated diphenylamine.
 23. Themethod as described in claim 21, wherein the secondary diarylamine has aconcentration of about 0.1 to 2.5 wt % in the lubricant composition. 24.The method as described in claim 21, wherein the oil soluble tungstencompound is present in an amount sufficient to provide about 20 to about4000 ppm of tungsten in the lubricant composition.
 25. The method asdescribed in claim 21, wherein the oil soluble tungsten compound ispresent in an amount sufficient to provide about 20-1000 ppm of tungstenin the lubricant composition.
 26. The method as described in claim 21,wherein the oil soluble phenothiazine has a concentration of about 0.05to 1.5 wt % in the lubricant composition.
 27. The method as described inclaim 21, further comprising including in the lubricating compositionadditional antioxidants selected from the group consisting ofcopper-containing antioxidants, sulfur containing antioxidants, phenolicantioxidants, and mixtures thereof.
 28. The method as described in claim27 wherein the copper salt is selected from the group of carboxylatesconsisting of naphthenates, oleates, stearates, dialkyldithiophospahtes,dialkyldithiocarbamates and mixtures thereof.
 29. The method asdescribed in claim 21, further comprising including in the lubricatingcomposition a dispersant, a detergent, a friction modifier, an antiwearadditive, a corrosion inhibitor, a metal deactivator, a fuel economyagent, and a viscosity index improver.
 30. The composition of claim 1,wherein the organoamine tungstate is the reaction product obtained froma reaction that is selected from the group of reactions consisting of 1)the reaction of JMT tert-alkyl primary aliphatic amine and ammoniumortho tungstate; 2) the reaction of JMT tert-alkyl primary aliphaticamine and ammonium para tungstate; 3) the reaction of Primene JMTtert-alkyl primary aliphatic amine sulfate and sodiumtungstatedihydrate; 4) the reaction of JMT tert-alkyl primary aliphaticamine and tungstic acid hydrate derived from the reaction of sodiumtungstate dihydrate with acid; 5) the reaction of ditridecylamine andammonium orthotungstate; 6) the reaction of ditridecylamine and ammoniumparatungstate; 7) the reaction of ditridecylamine sulfate and sodiumtungstate dihydrate; 8) the reaction of ditridecylamine and tungsticacid hydrate derived from the reaction of sodium tungstate dihydratewith acid; 9) the reaction of Primene 81R tert-alkyl primary aliphaticamine and ammonium ortho tungstate; 10) the reaction of Primene 81Rtert-alkyl primary aliphatic amine and ammonium paratungstate; 11) thereaction of Primene 81R tert-alkyl primary aliphatic amine sulfate andsodium tungstate dihydrate; 12) the reaction of Primene 81R tert-alkylprimary aliphatic amine and tungstic acid hydrate derived from thereaction of sodium tungstate dihydrate with acid; 13) the reaction of asalt of N-oleyl-1,3-propanediamine with dinonyl naphthalene sulfonicacid and ammonium orthotungstate. 14) the reaction of a salt ofN-oleyl-1,3-propanediamine with dinonyl naphthalene sulfonic acid andammonium paratungstate. 15) the reaction of a salt ofN-oleyl-1,3-propanediamine with dinonyl naphthalene sulfonic acid andtungstic acid hydrate derived from the reaction of sodium tungstatedihydrate with acid; 16) the reaction of a salt ofN-oleyl-1,3-propanediamine with didodecyl naphthalene sulfonic acid andammonium paratungstate; 17) the reaction of a salt ofN-oleyl-1,3-propanediamine with didodecyl naphthalene sulfonic acid andammonium orthotungstate; 18) the reaction of a salt ofN-oleyl-1,3-propanediamine with didodecyl naphthalene sulfonic acid andtungstic acid hydrate derived from the reaction of sodium tungstatedihydrate with acid; 19) the reaction of a salt ofN-oleyl-1,3-propanediamine with naphthenic acid and ammoniumparatungstate; 20) the reaction of a salt of N-oleyl-1,3-propanediaminewith naphthenic acid and ammonium orthotungstate. 21) the reaction of asalt of N-oleyl-1,3-propanediamine with naphthenic acid and tungsticacid hydrate derived from the reaction of sodium tungstate dihydratewith acid. 22) the reaction of N-oleyl-1,3-propanediamine with canolaoil and ammonium paratungstate; 23) the reaction ofN-oleyl-1,3-propanediamine with canola oil and ammonium orthotungstate;24) the reaction of N-oleyl-1,3-propanediamine with canola oil andtungstic acid hydrate derived from the reaction of sodium tungstatedihydrate with acid. 25) the reaction of aminoethyl imidazoline withdidodecyl naphthalene sulfonic acid and ammonium paratungstate; 26) thereaction of aminoethyl imidazoline with didodecyl naphthalene sulfonicacid and ammonium ortho tungstate; 27) the reaction of aminoethylimidazoline with didodecyl naphthalene sulfonic acid and tungstic acidhydrate derived from the reaction of sodium tungstate dihydrate withacid; 28) the reaction of alkenyl succinic anhydride withdiethylenetriamine and ammonium paratungstate; 29) the reaction ofalkenyl succinic anhydride with diethylenetriamine and ammoniumorthotungstate; 30) the reaction of alkenyl succinic anhydride withdiethylenetriamine and tungstic acid hydrate derived from the reactionof sodium tungstate dihydrate with acid; 31) the reaction ofbis(2-hydroxyethyl)cocoalkylamine and ammonium orthotungstate; 32) thereaction of bis(2-hydroxyethyl)cocoalkylamine and ammoniumparatungstate; 33) the reaction of bis(2-hydroxyethyl)cocoalkylamine andtungstic acid hydrate derived from the reaction of sodium tungstatedihydrate with acid; 34) the reaction ofbis(2-hydroxyethyl)cocoalkylamine sulfate and sodium tungstatedehydrate; 35) the reaction of a salt of N-oleyl-1,3-propanediamine withdi(2-ethylhexyl)phosphate and ammonium orthotungstate; 36) the reactionof a salt of N-oleyl-1,3-propanediamine with di(2-ethylhexyl)phosphateand ammonium paratungstate; 37) the reaction of a salt ofN-oleyl-1,3-propanediamine with di(2-ethylhexyl)phosphate and tungsticacid hydrate derived from the reaction of sodium tungstate dihydratewith acid; 38) the reaction of a salt of N-oleyl-1,3-propanediamine withdi(2-ethylhexyl)dithio phosphate and ammonium orthotungstate; 39) thereaction of a salt of N-oleyl-1,3-propanediamine withdi(2-ethylhexyl)dithio phosphate and ammonium orthotungstate; and 40)the reaction of a salt of salt of N-oleyl-1,3-propanediamine withdi(2-ethylhexyl)dithio phosphate and tungstic acid hydrate derived fromthe reaction of sodium tungstate dihydrate with acid. 41) the reactionof a salt of N-oleyl-1,3-propanediamine with di(oleyl)phosphate andammonium orthotungstate; 42) the reaction of a salt ofN-oleyl-1,3-propanediamine with di(oleyl)phosphate and ammoniumparatungstate; 43) the reaction of a salt of N-oleyl-1,3-propanediaminewith di(oleyl)phosphate and tungstic acid hydrate derived from thereaction of sodium tungstate dihydrate with acid;
 31. A lubricating oiladditive compound prepared by the process comprising reacting a tungstencontaining precursor with an amine selected from the group consistingof: (a) polyamines of the formula:

wherein R₇, R₈ and R₉ are each hydrogen; C₁ to C₂₅ straight or branchedchain alkyl radicals; C₁ to C₁₂ alkoxy-(C₆ alkylene) radicals; C₂ to C₁₂alkylamino-C₂ to C₆ alkylene) radicals; each s can be the same or adifferent number of from 2 to 6, and t is a number from 0 to 10, and atleast one of R₇, R₈ and R₉ must be hydrogen; (b) an N-aminoalkylpiperazine of the formula:

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3; (c) imidazolines of the formula:

in which n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, or substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, an aryl, aralkyl, cycloalkyl or heterocyclic radical,substituted if desired with halogen, nitro groups, alkyl groups, alkoxygroups or amino groups, and, when m=1 represents hydrogen; (d) a sulfurcontaining amine, (e) an aminosilane of the formula:

wherein R₁₇ and R₁₈ independently of one another are hydrogen, C₁-C₂₅alkyl, 2-hydroxyethyl, C₃-C₂₅ alkyl which is interrupted by oxygen orsulfur; C₂-C₂₄ alkenyl or

R₁₉ is C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen orsulfur; hydroxyl, C₁-C₁₈ alkoxy or C₂-C₂₄ alkenyl, R₂₀ is hydroxyl,C₁-C₁₈ alkoxy or C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur;and, if a and b together are 1, three radicals R₂₀ together are N(CH₂CH₂O—)₃, X₂ is C₁-C₁₈ alkylene, C₂-C₂₀ alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈ cycloalkylene, phenylene or naphthylene which isunsubstituted or substituted by C₁-C₄ alkyl; or is C₄-C₁₈ alkylene whichis interrupted by oxygen, sulfur or

R₂₁ is hydrogen or C₁-C₈ alkyl with the proviso that two nitrogen atomsare not attached to the same carbon atom, a is 1 or 2, and b is 0, 1 or2; (f) an ethoxylated amine of formula:

where Z, is straight or branched chain alkyl of from about 8 to about 26carbon atoms, alkoxy alkyl of 4 to 22 carbon atoms and n=2 to about 50,and x₁=from about 1 to about
 49. (g) an alkylated phenothiazine of theformula:

wherein R₁₁ and R₁₂ are hydrogen or together form a fused six-memberaromatic ring; one of R₁₃ and R₁₄ is hydrogen and the other is C₂-C₃₀alkyl, cyclo-C₅-C₁₂ alkyl, —C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl orα,α-dimethylbenzyl; or both R₁₃ and R₁₄ are C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ hydrogen; or R₁₃ is hydrogen and R₁₄ is C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ together form a fused six-member aromatic ring, R₁₅ is hydrogen,C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or a group —CH₂SR₄, whereR₄ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or an alkylene, aralkylenebridging two phenothiazine moieties; (h) an alkylated diarylamine of theformula:

wherein R₂₂ and R₂₃ each independently represents a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms, R₂₄ ishydrogen, C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or a group—CH₂SR₅, where R₅ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or analkylene, aralkylene bridging two amine moieties; (i) a triazole of theformula:

wherein R₂₅ is hydrogen or a C₁-C₂₀ alkyl residue, R₂₆ and R₂₇ are thesame or different and each is H, C₁-C₂₀ alkyl, C₃-C₂₀ alkenyl, C₅-C₁₂cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆ and R₂₇, together withthe nitrogen atom to which they are attached, form a 5-, 6- or7-membered heterocyclic residue or R₂₆ and R₂₇ is each a residue offormula:R₂₈X₃[(alkylene)O]_(n1)(alkylene)- wherein X₃ is O, S or N(R₂₈), R₂₈ ishydrogen or C₁-C₂₀ alkyl, “alkylene” is a C₁-C₁₂ alkylene residue and n₁is 0 or an integer from 1 to 6, R₃₀ is hydrogen, C₁-C₂₀ alkyl or C₆-C₁₀aryl or C₇-C₁₈ alkyl phenyl; and R₃₁ is hydrogen, C₁-C₂₀ alkyl or aresidue —CH₂ NR₂₆R₂₇ wherein R₂₆ and R₂₇ have their previoussignificance or R₂₆ has its previous significance and R₂₇ is a residueof formula:

or R₂₇ is a residue of formula as defined above and R₂₆ is a residue offormula:-[alkylene]_(n1)-N(R₃₂)_A₋[N(R₃₂)₂]_(m1) wherein m₁ is 0 or 1 and, whenm₁ is 0, A is a residue of formula (I) and, when m₁ is 1, A is alkyleneor C₆-C₁₀ arylene, and R₃₂ is a residue of formula I; (j) a substitutedphenol of the formula:

wherein R₄₁ and R₄₂ are independently alkyl of 1 to 18 carbon atoms,cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alkylof 1 to 18 carbon atoms, aralkyl of 7 to 9 carbon atoms or said aralkylsubstituted by alkyl of 1 to 18 carbon atoms, R₂₆ and R₂₇ are the sameor different and each is H, C₁-C₂₀ alkyl, C₃-C₂₀ alkenyl, C₅-C₁₂cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆ and R₂₇ together with thenitrogen atom to which they are attached, form a 5-, 6- or 7-memberedheterocyclic residue or R₂₆ and R₂₇ is each a residue of formula:R₂₈X₃[(alkylene)O]_(n1)(alkylene)- wherein X₃ is O, S or N(R₂₈), R₂₈ ishydrogen or C₁-C₂₀ alkyl, “alkylene” is a C₁-C₁₂ alkylene residue and n₁is an integer from 0 to 6; k) a polyamine salt derived from the reactionof a polyamine and an acid, wherein said polyamine is selected from thegroup consisting of 1) a polyamine of the following formula

where x is 1 or 2, and R is an aliphatic or aromatichydrocarbon-containing group containing about 6 to about 30 carbonatoms; wherein R optionally may contain oxygen; 2) a polyamine of theformula

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3; 3) a polyamine of the formula

wherein n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, an aryl, aralkyl, cycloalkyl or heterocyclic radical,substituted if desired with halogen, nitro groups, alkyl groups, alkoxygroups or amino groups, and, when m=1, represents hydrogen;  and whereinsaid acid is selected from the group consisting of: 1) an alkylatedmonosulfonic acid of the formula

wherein R¹⁰ is H or an alkyl group containing up to 20 carbon atoms, andx is an integer from 0 to 2; 2) an alkylated aryl sulfonic acid of theformula

wherein R₅₁, R₅₂, R₅₃ and R₅₄ are individually selected from the groupconsisting of hydrogen or essentially linear hydrocarbyl groups havingabout 9 to about 22 carbon atoms; and wherein l, m, n and p are integersfrom 0 to 4 and the sum of l+m+n+p is at least 1; and wherein R₅₁, R₅₂,R₅₃ and R₅₄ is a hydrogen where either l, m, n, or p is 0; 3) analkylated aryl disulfonic acid of the formula

wherein each of R¹¹ and R¹² is the same or different and is a linear orbranched alkyl group with 6 to 16 carbons, y is 0 to 3, z is 0 to 3 withthe proviso that y+z is 1 to 4, n is 0 to 3, B is a divalent moietyselected from the group consisting of —C(R¹³)(R¹⁴)—, wherein each of R¹³and R¹⁴ is H or independently a linear or branched alkyl group of 1-4carbons and n is 1; —C(═O)—, wherein n is 1; —O— wherein n is 1; —S—,wherein n is 1 to 3; and —SO₂—, wherein n is 1; 4) a mixture ofnaphthenic acids, wherein said mixture of napthenic acids comprises amixture of monobasic acids of cycloparaffins derived from eithercyclopentane or cyclohexane and cyclopentane and homologs and highermolecular weight analogs, said napthenic acids having molecular weightsfrom about 180 to about 350; 5) dihydrocarbylphosphoric acids,dihydrocarbyldithiophosphoric acids, or dihydrocarbylmonothiophosphoricacids of the formula

wherein Y₁ and Y₂ are each independently S or O, and wherein R¹⁵ and R¹⁶are each independently H, C₃-C₁₈ alkyl, C₅-C₁₂ cycloalkyl, C₅-C₆cycloalkylmethyl, C₉-C₁₀ bicycloalkylmethyl, C₉-C₁₀ tricycloalkylmethyl,phenyl, C₇-C₂₄-alkylphenyl, i-propyl, i-butyl, 2-ethylhexyl, octylphenyl or oleyl or R¹⁵ and R¹⁶ together form a group of the partialformula,

a C₉-C₁₀ bicycloalkylmethyl, or a C₉-C₁₀ tricycloalkylmethyl of theformulae:

6) an alkyl phenoxyalkanoic acid of the formula

wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

7) an N-acyl sarcosine of the formula

wherein the acyl group R^(t)—C(═O)— is the residue of a fatty acidhaving 10 to 20 carbon atoms; 8) a long-chain monocarboxylic acid of8-100 carbon atoms; k) a reaction product of a long chain monocarboxylicacid, naphthenic acid, alkyl phenoxy alkanoic acid, N-acyl sarcosine orfatty oil, with a diamine, wherein the fatty oil is a triglyceride ofthe following formula:

where R, R′ and R″ independently represent saturated or unsaturatedaliphatic hydrocarbon groups having from about 8 to about 22 carbonatoms, wherein an alkyl phenoxyalkanoic acid is of the formula

 wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

wherein an N-acyl sarcosine is of the formula

 wherein the acyl group R^(t)—C(═O)— is the residue of a fatty acidhaving 10 to 20 carbon atoms; wherein the long-chain monocarboxylic acidcomprises 8-100 carbon atoms; wherein naphthenic acid comprises amixture of monobasic acids of cycloparaffins derived from eithercyclopentane or cyclohexane and cyclopentane and homologs and highermolecular weight analogs, said monobasic acid having molecular weightfrom about 180 to about 350;  and wherein the diamine of the followingformula:

 where x is 1 or 2, and R is an aliphatic or aromatichydrocarbon-containing group containing a about 6-24 carbon atoms;wherein R optionally may contain oxygen; l) Reaction product of asubstituted succinic anhydrides with a polyamine wherein said reactionproduct has the formula.

 wherein R¹⁸ is a C6 to C30 isomerized alkenyl group, represented by:

 (where g and h are integers whose sum is from 1 to 25), or its fullysaturated alkyl analog, R¹⁷ is an alkylamine group, arylamine group, andtheir heteroatom containing derivatives;  or said reaction product hasthe formula  or said reaction product has the formula

 wherein R²¹ and R²² may be identical or different from each other andare each saturated or unsaturated hydrocarbon groups having 5 to 40carbons; R²³ is a divalent hydrocarbon group having 1 to 5 carbons; R²⁴is a hydrogen atom or a hydrocarbon group having 1 to 20 carbons,cycloalkyl groups having 6 to 20 carbon atoms; and aryl groups having 6to 20 carbon atoms, and said aryl group substituted by alkyl groupshaving 1 to 12 carbon atoms, wherein said hydrocarbon groups optionallycontain from 1 to 5 of each amine and/or amide substituted alkyl groupsand wherein n is an integer in the range of 0 to
 10. 31. The aminetungstate lubricant additives of claim 30 derived from the reaction of asalt of N-oleyl-1,3-propanediamine with dinonyl naphthalene sulfonicacid; a salt of N-oleyl-1,3-propanediamine with didodecyl naphthalenesulfonic acid; a salt of N-oleyl-1,3-propanediamine with naphthenicacid; a reaction product of canola oil with N-oleyl-1,3-propanediamine areaction product of aminoethyl imidazoline with Didodecyl naphthalenesulfonic acid; a bis succinimide from alkenyl succinic anhydride anddiethylene triamine; bis(2-hydroxy ethyl)cocoamine and alkyl (C₁₄-C₁₈)bis(2-hydroxyethyl)amine, a salt of N-oleyl-1,3-propanediamine withdi(2-ethylhexyl)phosphonic acid; a salt of N-oleyl-1,3-propanediaminewith di(oleyl)phosphonic acid; or a salt of N-oleyl-1,3-propanediaminewith di(2-ethylhexyl)dithiophosphoric acid.
 32. A lubricating oiladditive compound prepared by the process comprising reacting of amolybdenum precursor compound with an amine selected from the groupconsisting of: (a) polyamines of the formula:

wherein R₇, R₈ and R⁹ are each hydrogen; C₁ to C₂₅ straight or branchedchain alkyl radicals; C₁ to C₁₂ alkoxy-(C₆ alkylene) radicals; C₂ to C₁₂alkylamino-C₂ to C₆ alkylene) radicals; each s can be the same or adifferent number of from 2 to 6; and t is a number from 0 to 10 and atleast one of R₇, R₈ and R₉ must be hydrogen; (b) an N-aminoalkylpiperazine of the formula:

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3; (c) imidazolines of the formula:

in which n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, or substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, an aryl, aralkyl, cycloalkyl or heterocyclic radical,substituted if desired with halogen, nitro groups, alkyl groups, alkoxygroups or amino groups, and, when m=1 represents hydrogen; (d) a sulfurcontaining amine, (e) an aminosilane of the formula:

wherein R₁₇ and R₁₈ independently hydrogen, C₁-C₂₅ alkyl,2-hydroxyethyl, C₃-C₂₅ alkyl which is interrupted by oxygen or sulfur;C₂-C₂₄ alkenyl or

R₁₉ is C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen orsulfur; hydroxyl, C₁-C₁₈ alkoxy or C₂-C₂₄ alkenyl, R₂₀ is hydroxyl,C₁-C₁₈ alkoxy or C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur;and, if a and b together are 1, three radicals R₂₀ together are N(CH₂CH₂O—)₃, X₂ is C₁-C₁₈ alkylene, C₂-C₂₀ alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈ cycloalkylene, phenylene or naphthylene which isunsubstituted or substituted by C₁-C₄ alkyl; or is C₄-C₁₈ alkylene whichis interrupted by oxygen, sulfur or

R₂₁ is hydrogen or C₁-C₈ alkyl with the proviso that two nitrogen atomsare not attached to the same carbon atom, a is 1 or 2, and b is 0, 1 or2; (f) An ethoxylated amine of formula:

where Z is straight or branched chain alkyl of from about 8 to about 26carbon atoms, alkoxy alkyl of 4 to 22 carbon atoms and n=2 to about 50,and x₁=from about 1 to about 49; (g) an alkylated phenothiazine of theformula:

wherein R₁₁ and R₁₂ are hydrogen or together form a fused six-memberaromatic ring, one of R₁₃ and R₁₄ is hydrogen and the other is C₂-C₃₀alkyl, cyclo-C₅-C₁₂ alkyl, —C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl orα,α-dimethylbenzyl; or both R₁₃ and R₁₄ are C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ hydrogen; or R₁₃ is hydrogen and R₁₄ is C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ together form a fused six-member aromatic ring, R₁₅ is hydrogen,C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or a group —CH₂SR₄, whereR₄ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or an alkylene, aralkylenebridging two phenothiazine moieties; (h) an alkylated diarylamine of theformula:

wherein R₂₂ and R₂₃ each independently represents a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms, R₂₄ ishydrogen, C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or a group—CH₂SR₅, where R₅ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or analkylene, aralkylene bridging two amine moieties; (i) a triazole of theformula:

wherein R₂₅ is hydrogen or a C₁-C₂₀ alkyl residue, R₂₆ and R₂₇ are thesame or different and each is H, C₁-C₂₀ alkyl, C₃-C₂₀ alkenyl, C₅-C₁₂cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆ and R₂₇, together withthe nitrogen atom to which they are attached, form a 5-, 6- or7-membered heterocyclic residue or R₂₆ and R₂₇ is each a residue offormula:R₂₈X₃[(alkylene)O]_(n1)(alkylene)- wherein X₃ is O, S or N(R₂₈), R₂₈ ishydrogen or C₁-C₂₀ alkyl, “alkylene” is a C₁-C₁₂ alkylene residue and n₁is 0 or an integer from 1 to 6, R₃₀ is hydrogen, C₁-C₂₀ alkyl or C₆-C₁₀aryl or C₇-C₁₈ alkyl phenyl; and R₃₁ is hydrogen, C₁-C₂₀ alkyl or aresidue —CH₂ NR₂₆R₂₇ wherein R₂₆ and R₂₇ have their previoussignificance or R₂₆ has its previous significance and R₂₇ is a residueof formula:

or R₂₇ is a residue of formula as defined above and R₂₆ is a residue offormula:-[alkylene]_(n1)-N(R₃₂)_A₋[N(R₃₂)₂]_(m1) wherein m₁ is 0 or 1 and, whenm₁ is 0, A is a residue of formula (I) and, when m₁ is 1, A is alkyleneor C₆-C₁₀ arylene, and alkylene and n₁ have their previous significanceand R₃₂ is a residue of formula I; (j) a substituted phenol of theformula:

wherein R₄₁, and R₄₂, are independently alkyl of 1 to 18 carbon atoms,cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alkylof 1 to 18 carbon atoms, aralkyl of 7 to 9 carbon atoms, wherein thearalkyl may be further substituted by alkyl of 1 to 18 carbon atoms, R₂₆and R₂₇ are the same or different and each is H, C₁-C₂₀ alkyl, C₃-C₂₀alkenyl, C₅-C₁₂ cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆ and R₂₇,together with the nitrogen atom to which they are attached, form a 5-,6- or 7-membered heterocyclic residue or R₂₆ and R₂₇ is each a residueof formula:R₂₈X₃[(alkylene)O]_(n1)(alkylene)- wherein X₃ is O, S or N(R₂₈), R₂₈ ishydrogen or C₁-C₂₀ alkyl, “alkylene” is a C₁-C₁₂ alkylene residue and n₁is 0 or an integer from 1 to 6; j) a polyamine salt derived from thereaction of a polyamine and an acid, wherein the polyamine in selectedfrom the group consisting of 1) a polyamine of the formula

where x is 1 or 2, and R is an aromatic on aliphatichydrocarbon-containing group containing about 6-24 carbon atoms, whereinR optionally may also contain oxygen, 2) a polyamine of the formula

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3; 3) a polyamine of the formula

wherein n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, or substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, an aryl, aralkyl, cycloalkyl or heterocyclic radical,substituted if desired with halogen, nitro groups, alkyl groups, alkoxygroups or amino groups, and, when m=1 represents hydrogen; and whereinsaid acid is selected from the group consisting of 1) an alkylatedmonosulfonic acid, of the formula

wherein R¹⁰ is H or an alkyl group containing up to 20 carbon atoms, andx is an integer from 0 to 2; 2) an alkylated aryl sulfonic acid of theformula

wherein R₅₁, R₅₂, R₅₃ and R₅₄ are individually selected from the groupconsisting of hydrogen or essentially linear hydrocarbyl groups havingabout 9 to about 22 carbon atoms; and wherein l, m, n and p are integersfrom 0 to 4 and the sum of l+m+n+p is at least 1; and wherein R₅₁, R₅₂,R₅₃ and R₅₄ is a hydrogen where either l, m, n, or p is 0; 3) alkylatedaryl disulfonic acids of the formula

wherein each of R¹¹ and R¹² is the same or different and is a linear orbranched alkyl group with 6 to 16 carbons, y is 0 to 3, z is 0 to 3 withthe proviso that y+z is 1 to 4, n is 0 to 3, B is a divalent moietyselected from the group consisting of —C(R¹³)(R¹⁴)—, wherein each of R¹³and R¹⁴ is H or independently a linear or branched alkyl group of 1-4carbons and n is 1; —C(═O)—, wherein n is 1; —O— wherein n is 1; —S—,wherein n is 1 to 3; and —SO₂—, wherein n is 1; 4) a mixture ofnaphthenic acids, wherein said mixture of napthenic acids comprises amixture of monobasic acids of cycloparaffins derived from eithercyclopentane or cyclohexane and cyclopentane and homologs and highermolecular weight analogs, said napthenic acids having molecular weightsfrom about 180 to about 350; 5) dihydrocarbylphosphoric acids,dihydrocarbyldithiophosphoric acids, or dihydrocarbylmonothiophosphoricacids of the formula

wherein Y₁ and Y₂ are each independently S or O, and wherein R¹⁵ and R¹⁶are each independently H, C₃-C₁₈ alkyl, C₅-C₁₂ cycloalkyl, C₅-C₆cycloalkylmethyl, C₉-C₁₀ bicycloalkylmethyl, C₉-C₁₀ tricycloalkylmethyl,phenyl, C₇-C₂₄-alkylphenyl, i-propyl, i-butyl, 2-ethylhexyl, octylphenyl or oleyl or R¹⁵ and R¹⁶ together form a group of the partialformula,

a C₉-C₁₀ bicycloalkylmethyl, or a C₉-C₁₀ tricycloalkylmethyl of theformulae:

6) an alkyl phenoxyalkanoic acid of the formula

wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

7) an N-acyl sarcosine of the formula

wherein the acyl group R^(t)—C(═O)— is the residue of a fatty acidhaving 10 to 20 carbon atoms; 8) a long-chain monocarboxylic acid of8-100 carbon atoms; k) a reaction product of naphthenic acid, an alkylphenoxy alkanoic acid or N-acyl sarcosine with a diamine of thefollowing formula:

where x is 1 or 2, and R is an aliphatic or aromatichydrocarbon-containing group containing a about 6-24 carbon atoms.wherein R optionally may contain contain oxygen; wherein the alkylphenoxyalkanoic acid is of the formula

wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

and wherein an N-acyl sarcosine is of the formula

where the acyl group R^(t)—C(═O)— is the residue of a fatty acid having10 to 20 carbon atoms; wherein naphthenic acid comprises a mixture ofmonobasic acids of cycloparaffins derived from either cyclopentane orcyclohexane and cyclopentane and homologs and higher molecular weightanalogs, said monobasic acids having molecular weight from about 180 toabout 350; l) a reaction product of a substituted succinic anhydridewith a polyamine, wherein said reaction product has the formula

where R¹⁸ is a C6 to C30 isomerized alkenyl group, represented by:

where g and h are integers whose sum is from 1 to 25, or its fullysaturated alkyl analog, R¹⁷ is an alkylamine group, arylamine group, andtheir heteroatom containing derivatives; or wherein said reactionproduct has the formula

wherein, R²¹ and R²² may be identical or different from each other andare each saturated or unsaturated hydrocarbon groups having 5 to 40carbons; R²³ is a divalent hydrocarbon group having 1 to 5 carbons; R²⁴is a hydrogen atom or a hydrocarbon group having 1 to 20 carbons,cycloalkyl groups having 6 to 20 carbon atoms; aryl groups having 6 to20 carbon atoms, and where said aryl group optionally may be substitutedby alkyl groups having 1 to 12 carbon atoms, and said hydrocarbon groupscontain from 1 to 5 of each amine and/or amide substituted alkyl groupsand n is an integer in the range of 0 to
 10. 33. A lubricating oiladditive amine molybdate of claim 32 derived from the reaction of a saltof N-oleyl-1,3-propanediamine with dinonyl naphthalene sulfonic acid, asalt of N-oleyl-1,3-propanediamine with didodecyl naphthalene sulfonicacid, a salt of N-oleyl-1,3-propanediamine with naphthenic acid, areaction product of canola oil with N-oleyl-1,3-propanediamine, areaction product of aminoethyl imidazoline with Didodecyl naphthalenesulfonic acid, bis succinimide from alkenyl succinic anhydride anddiethylene triamine, bis(2-hydroxy ethyl)cocoamine and alkyl (C₁₄-C₁₈)bis(2-hydroxyethyl)amine, a salt of N-oleyl-1,3-propanediamine withdi(2-ethylhexyl)phosphonic acid, a salt of N-oleyl-1,3-propanediaminewith di(oleyl)phosphonic acid, a salt of N-oleyl-1,3-propanediamine withdi(2-ethylhexyl)dithiophosphoric acid.
 34. A lubricating oil additivecomposition comprising lubricating oil in an amount greater than 50% byweight; an oil soluble secondary diaryl amine, and/or an oil solublealkylated phenothiazine; and an oil soluble or oil dispersiblemolybdenum compound wherein the oil soluble or oil dispersiblemolybdenum compound comprises an organo molybdate or an amine molybdatederived from amines selected from the group consisting of: (a)polyamines of the formula:

wherein R₇, R₈ and R₉ are each hydrogen; C₁ to C₂₅ straight or branchedchain alkyl radicals; C₁ to C₁₂ alkoxy-(C₆ alkylene) radicals; C₂ to C₁₂alkylamino-C₂ to C₆ alkylene) radicals; each s can be the same or adifferent number of from 2 to 6; and t is a number from 0 to 10 and atleast one of R₇, R₈ and R₉ must be hydrogen; (b) an N-aminoalkylpiperazine of the formula:

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3; (c) imidazolines of the formula:

in which n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, or substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, an aryl, aralkyl, cycloalkyl or heterocyclic radical,substituted if desired with halogen, nitro groups, alkyl groups, alkoxygroups or amino groups, and when m=1 represents hydrogen, (d) a sulfurcontaining amine, (e) an aminosilane of the formula:

wherein R₁₇ and R₁₈ independently of one another are hydrogen, C₁-C₂₅alkyl, 2-hydroxyethyl, C₃-C₂₅ alkyl which is interrupted by oxygen orsulfur; C₂-C₂₄ alkenyl or

R₁₉ is C₁-C₂₅ alkyl, C₂-C₂₅ alkyl which is interrupted by oxygen orsulfur; hydroxyl, C₁-C₁₈ alkoxy or C₂-C₂₄ alkenyl, R₂₀ is hydroxyl,C₁-C₁₈ alkoxy or C₂-C₁₈ alkoxy which is interrupted by oxygen or sulfur;and, if a and b together are 1, three radicals R₂₀ together are N(CH₂CH₂O—)₃, X₂ is C₁-C₁₈ alkylene, C₂-C₂₀ alkylidene, C₇-C₂₀phenylalkylidene, C₅-C₈ cycloalkylene, phenylene or naphthylene which isunsubstituted or substituted by C₁-C₄ alkyl; or is C₄-C₁₈ alkylene whichis interrupted by oxygen, sulfur or

R₂₁ is hydrogen or C₁-C₈ alkyl with the proviso that two nitrogen atomsare not attached to the same carbon atom, a is 1 or 2, and b is 0, 1 or2; (f) an ethoxylated amine of formula:

where Z, is straight or branched chain alkyl of from about 8 to about 26carbon atoms, alkoxy alkyl of 4 to 22 carbon atoms and n=2 to about 50,and x₁=from about 1 to about
 49. (g) an alkylated phenothiazine of theformula:

wherein R₁₁ and R₁₂ are hydrogen or together form a fused six-memberaromatic ring, one of R₁₃ and R₁₄ is hydrogen and the other is C₂-C₃₀alkyl, cyclo-C₅-C₁₂ alkyl, —C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl orα,α-dimethylbenzyl; or both R₁₃ and R₁₄ are C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ hydrogen; or R₁₃ is hydrogen and R₁₄ is C₂-C₃₀ alkyl, cyclo-C₅-C₁₂alkyl-C₂-C₄ alkyl, α-C₁-C₂ alkylbenzyl or α,α-dimethylbenzyl, if R₁₁ andR₁₂ together form a fused six-member aromatic ring, R₁₅ is hydrogen,C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or a group —CH₂SR₄, whereR₄ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or an alkylene, aralkylenebridging two phenothiazine moieties; (h) an alkylated diarylamine of theformula:

wherein R₂₂ and R₂₃ each independently represents a substituted orunsubstituted aryl group having from 6 to 30 carbon atoms, R₂₄ ishydrogen, C₁-C₁₂ alkyl, benzyl, allyl, methallyl, phenyl or a group—CH₂SR₅, where R₅ is C₄-C₁₈ alkyl, —CH₂CH₂COO(C₄-C₁₈ alkyl), or analkylene, aralkylene bridging two amine moieties; (i) a triazole of theformula:

wherein R₂₅ is hydrogen or a C₁-C₂₀ alkyl residue, R₂₆ and R₂₇ are thesame or different and each is H, C₁-C₂₀ alkyl, C₃-C₂₀ alkenyl, C₅-C₁₂cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆ and R₂₇, together withthe nitrogen atom to which they are attached, form a 5-, 6- or7-membered heterocyclic residue or R₂₆ and R₂₇ is each a residue offormula:R₂₈X₃[(alkylene)O]_(n1)(alkylene)- wherein X₃ is O, S or N(R₂₈), R₂₈ ishydrogen or C₁-C₂₀ alkyl, “alkylene” is a C₁-C₁₂ alkylene residue and n₁is 0 or an integer from 1 to 6, R₃₀ is hydrogen, C₁-C₂₀ alkyl or C₆-C₁₀aryl or C₇-C₁₈ alkyl phenyl; and R₃₁ is hydrogen, C₁-C₂₀ alkyl or aresidue —CH₂ NR₂₆R₂₇ wherein R₂₆ and R₂₇ have their previoussignificance or R₂₆ has its previous significance and R₂₇ is a residueof formula:

or R₂₇ is a residue of formula as defined above and R₂₆ is a residue offormula:-[alkylene]_(n1)-N(R₃₂)_A₋[N(R₃₂)₂]_(m1) wherein m₁ is 0 or 1 and, whenm₁ is 0, A is a residue of formula (I) and, when m₁ is 1, A is alkyleneor C₆-C₁₀ arylene, and alkylene and n₁ have their previous significanceand R₃₂ is a residue of formula I, as defined above a substituted phenolof the formula:

wherein R₄₁, and R₄₂, are independently alkyl of 1 to 18 carbon atoms,cycloalkyl of 5 to 6 carbon atoms, phenyl, phenyl substituted by alkylof 1 to 18 carbon atoms, aralkyl of 7 to 9 carbon atoms, wherein thearalkyl optionally may be substituted by alkyl of 1 to 18 carbon atoms,R₂₆ and R₂₇ are the same or different and each is H, C₁-C₂₀ alkyl,C₃-C₂₀ alkenyl, C₅-C₁₂ cycloalkyl, C₇-C₁₃ aralkyl, C₆-C₁₀ aryl or R₂₆and R₂₇, together with the nitrogen atom to which they are attached,form a 5-, 6- or 7-membered heterocyclic residue or R₂₆ and R₂₇ is eacha residue of formula:R₂₈X₃[(alkylene)O]_(n1)(alkylene)- wherein X₃ is O, S or N(R₂₈), R₂₈ ishydrogen or C₁-C₂₀ alkyl, “alkylene” is a C₁-C₁₂ alkylene residue and n₁is an integer from 0 to 6; j) a polyamine salt obtained by the reactionof a polyamine and an acid, wherein said polyamine is selected from thegroup consisting of 1) a polyamine with the formula

where x is 1 or 2, and R is an aliphatic or aromatichydrocarbon-containing group containing a minimum of about 6-24 carbonatoms; wherein R optionally contains oxygen, 2) a polyamine with theformula

wherein p₁ and p₂ are the same or different and each is an integer from1 to 4, and e, f and o are the same or different and each is an integerfrom 1 to 3; 3) a polyamine with the formula

wherein n=2 or 3, m=1 or 2, R^(a), R^(b) and R^(c) are identical ordifferent, and represent hydrogen, alkyl, or substituted alkyl,hydroxyalkyl, aryl, aralkyl, cycloalkyl, heterocyclics, ether,thioether, halogen, —N(R)₂, polyethylene polyamines, nitro groups, ketogroups, ester groups, or carbonamide groups, alkyl substituted with thevarious functional groups described above, and T represents alkyl,alkylene, an aryl, aralkyl, cycloalkyl or heterocyclic radical,substituted if desired with halogen, nitro groups, alkyl groups, alkoxygroups or amino groups, and, when m=1 represents hydrogen, and whereinthe acid is selected from the group consisting of 1) an alkylatedmonosulfonic acid of the formula

wherein R¹⁰ is H or an alkyl group containing up to 20 carbon atoms, andx is an integer from 0 to 2; 2) an alkylated aryl sulfonic acid of theformula

wherein R₅₁, R₅₂, R₅₃ and R₅₄ are individually selected from the groupconsisting of hydrogen or essentially linear hydrocarbyl groups havingabout 9 to about 22 carbon atoms; and wherein l, m, n and p are integersfrom 0 to 4 and the sum of l+m+n+p is at least 1; and wherein R₅₁, R₅₂,R₅₃ and R₅₄ is a hydrogen where either l, m, n, or p is 0; 3) analkylated aryl disulfonic acids of the formula

wherein each of R¹¹ and R¹² is the same or different and is a linear orbranched alkyl group with 6 to 16 carbons, y is 0 to 3, z is 0 to 3 withthe proviso that y+z is 1 to 4, n is 0 to 3, B is a divalent moietyselected from the group consisting of —C(R¹³)(R¹⁴)—, wherein each of R¹³and R¹⁴ is H or independently a linear or branched alkyl group of 1-4carbons and n is 1; —C(═O)—, wherein n is 1; —O— wherein n is 1; —S—,wherein n is 1 to 3; and —SO₂—, wherein n is 1; 4) a mixture ofnaphthenic acids, wherein said mixture of napthenic acids comprises amixture of monobasic acids of cycloparaffins derived from eithercyclopentane or cyclohexane and cyclopentane and homologs and highermolecular weight analogs, said napthenic acids having molecular weightsfrom about 180 to about 350; 5) dihydrocarbylphosphoric acids,dihydrocarbyldithiophosphoric acids, or dihydrocarbylmonothiophosphoricacids of the formula

wherein Y₁ and Y₂ are each independently S or O, and wherein R¹⁵ and R¹⁶are each independently H, C₃-C₁₈ alkyl, C₅-C₁₂ cycloalkyl, C₅-C₆cycloalkylmethyl, C₉-C₁₀ bicycloalkylmethyl, C₉-C₁₀ tricycloalkylmethyl,phenyl, C₇-C₂₄-alkylphenyl, i-propyl, i-butyl, 2-ethylhexyl, octylphenyl or oleyl or R¹⁵ and R¹⁶ together form a group of the partialformula,

a C₉-C₁₀ bicycloalkylmethyl, or a C₉-C₁₀ tricycloalkylmethyl of theformulae:

6) an alkyl phenoxyalkanoic acid of the formula

wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

7) an N-acyl sarcosine of the formula

wherein the acyl group R^(t)—C(═O)— is the residue of a fatty acidhaving 10 to 20 carbon atoms; 8) a long-chain monocarboxylic acid of8-100 carbon atoms; k) a reaction product of naphthenic acid, an alkylphenoxy alkanoic acid or N-acyl sarcosine with a diamine of thefollowing formula:

where x is 1 or 2, and R is an aliphatic or aromatichydrocarbon-containing group containing a about 6-24 carbon atoms.wherein R optionally may contain oxygen; wherein the alkylphenoxyalkanoic acid is of the formula

wherein R^(q), R^(r), R^(s), R^(t) and R^(u) are, each independently ofthe other, hydrogen or C₁-C₂₀ alkyl and Q is a divalent C₁-C₂₀hydrocarbon radical, saturated or unsaturated, selected from the groupconsisting of

and wherein an N-acyl sarcosine is of the formula

where the acyl group R^(t)—C(═O)— is the residue of a fatty acid having10 to 20 carbon atoms; wherein naphthenic acid comprises a mixture ofmonobasic acids of cycloparaffins derived from either cyclopentane orcyclohexane and cyclopentane and homologs and higher molecular weightanalogs, said monobasic acids having molecular weight from about 180 toabout 350; l) a reaction product of a substituted succinic anhydridewith a polyamine, wherein said reaction product has the formula

where R¹⁸ is a C6 to C30 isomerized alkenyl group, represented by:

where g and h are integers whose sum is from 1 to 25, or its fullysaturated alkyl analog, R¹⁷ is an alkylamine group, arylamine group, andtheir heteroatom containing derivatives; or wherein said reactionproduct has the formula

wherein, R²¹ and R²² may be identical or different from each other andare each saturated or unsaturated hydrocarbon groups having 5 to 40carbons; R²³ is a divalent hydrocarbon group having 1 to 5 carbons; R²⁴is a hydrogen atom or a hydrocarbon group having 1 to 20 carbons,cycloalkyl groups having 6 to 20 carbon atoms; aryl groups having 6 to20 carbon atoms, and where said aryl group optionally may be substitutedby alkyl groups having 1 to 12 carbon atoms, and said hydrocarbon groupscontain from 1 to 5 of each amine and/or amide substituted alkyl groupsand n is an integer in the range of 0 to
 10. 35. A lubricating oilcomposition of claim 34, wherein the amine molybdate is derived from areaction of a salt of N-oleyl-1,3-propanediamine with dinonylnaphthalene sulfonic acid; a salt of N-oleyl-1,3-propanediamine withdidodecyl naphthalene sulfonic acid; a salt ofN-oleyl-1,3-propanediamine with naphthenic acid; a reaction product ofcanola oil with N-oleyl-1,3-propanediamine; a reaction product ofaminoethyl imidazoline with didodecyl naphthalene sulfonic acid; bissuccinimide from alkenyl succinic anhydride and diethylene triamine;bis(2-hydroxy ethyl)cocoamine, alkyl (C₁₄-C₁₈) bis(2-hydroxyethyl)amine;a salt of N-oleyl-1,3-propanediamine with di(2-ethylhexyl)phosphonicacid; a salt of N-oleyl-1,3-propanediamine with di(oleyl)phosphonicacid, or a salt of N-oleyl-1,3-propanediamine withdi(2-ethylhexyl)dithiophosphoric acid.